Novel extension functionalization strategy for catchment type MOF (Metal Organic Framework)

Abstract

Novel water stable metal organic framework (MOF) compositions with linker extension / functionalization provide higher water absorption at low relative humidity.

Description

[0001] This invention was made with government support under Grant No. HR0011-21-C-002 from the Department of Defense Advanced Research Projects Agency. The government has certain rights in this invention.

[0002] introduce

[0003] Nearly one-third of the world's population lives in drylands with limited access to clean water. 1 Therefore, new solutions are urgently needed to address the global water crisis that affects millions of people. Atmospheric water accounts for 10% of 18 cubic meters, which constitutes 3% of the total fresh water available on our planet. 2 This water exists everywhere and at all times, and once collected, it could help alleviate the global water crisis. 3

[0004] Metal-organic frameworks (MOFs) have emerged as promising materials for atmospheric water capture. 4,5 To this end, several MOFs have been shown to exhibit three main features: 1) high water stability, 2) a steep water uptake step at low relative humidity (RH) (<40%), and 3) low regeneration energy for recycling purposes. Importantly, unlike other porous materials 6 Through modification at the molecular level, MOFs show high potential for tunability of pore volume, pore structure and surface area, which directly affects their water absorption properties. Enhancing water absorption at low RH while maintaining all the above characteristics is a long-standing problem in the study of water-harvesting MOFs.

[0005] In addition to MOFs, various materials such as silica gel, porous polymers and zeolites were tested for their water absorption properties. 10 . However, they all suffer from drawbacks that hamper their use in water collection devices. Thus, although zeolites exhibit a steep water absorption at low pH values, they require a large amount of energy for regeneration. Otherwise, they undergo structural poisoning by permanent water entrapment in their pores, which has a negative impact on their efficacy. The water absorption isotherm curves of silica gels and porous polymers lack steepness, resulting in a low working capacity of these materials.

[0006] Among MOFs, only a few examples have shown ideal properties for water harvesting applications. 11 Moisture sensitivity and hydrophobicity of most MOF structures are persistent issues. 12 Therefore new types of structures are highly needed. Summary of the invention

[0007] Herein, we report a new water-stable MOF that has higher water uptake at low RH compared to its previous analogs. 7,8,9 In the present disclosure, we introduce a linker extension / functionalization strategy to obtain MOF structures with enhanced water absorption capacity. Linker extensions, where at least one of m or n is 1-5, provide MOFs with enhanced pore size and volume. In addition, further customized extended linkers can be used to tune or adjust the water absorption properties of the corresponding MOFs by changing their heterocyclic cores (X, Y, Z, I) or by introducing substituents (R1-R5).

[0008] The disclosed linker extension / functionalization strategy can be used to increase the water uptake of existing MOFs without significantly negatively affecting their lifetime and hydrophilicity.

[0009] The targeted purpose of the linker extension / functionalization strategy is to increase the water uptake of MOFs for deployment in water harvesting devices. Compared to previously used MOFs, this application allows the use of less material to capture the same amount of water at a desired RH.

[0010] Furthermore, additional modifications of the extended linker provide a variety of MOF structures with different water-harvesting properties. Therefore, in addition to water-harvesting devices, dehumidifiers, heat pumps, adsorption chillers, and other equipment can also benefit from the use of these new MOF structures.

[0011] In one aspect, the present invention provides novel water-stable metal-organic framework (MOF) compositions (with linker extension / functionalization) that provide higher water absorption at low relative humidity.

[0012] In one aspect, the present invention provides a metal-organic framework (MOF) composition comprising a metal complexed with a linker of the formula

[0013]

[0014] in

[0015] X, Y, and Z are independently C(H), N(H), O, or S;

[0016] R1-R5 are independently CH3, NH2, OH, halogen or H;

[0017] m is an integer from 0 to 5;

[0018] n is an integer from 1 to 5;

[0019] l is an integer of 1 or 2; and

[0020] b1 and b2 are independently a single bond or a double bond; and

[0021] At least one b2 is a double bond.

[0022] In one aspect, the present invention provides a metal-organic framework (MOF) comprising a repeating core, wherein the core comprises a secondary structural unit connected to an organic ligand (linker), wherein the secondary structural unit comprises one or more metals or metal-containing complexes, wherein the organic ligand (linker) has formula I (as above), and wherein the secondary structural unit is connected to the organic ligand via an oxygen atom of a carboxylate group in the organic ligand (linker).

[0023] In the implementation:

[0024] R1-R5 are H; or

[0025] 1, 2, 3, 4 or 5 of R1-R5 are CH3, NH2, H or halogen.

[0026] m is 0, 1 or 2 and n is 1, 2 or 3;

[0027] m is 0, 1 or 2 and n is 1 or 2;

[0028] m is 0, and n is 1;

[0029] m is 0, and n is 2;

[0030] m is 1, and n is 1;

[0031] m is 1, and n is 2;

[0032] m is 1, and n is 3;

[0033] m is 2, and n is 2;

[0034] m is 2, and n is 3; or

[0035] m is 3, and n is 3.

[0036] l is 1.

[0037] 1, 2, or 3 of X, Y, and Z are independently N(H), O, or S; or

[0038] X and Y are N and NH, respectively, and Z is C.

[0039] In embodiments, the MOF composition comprises a linker of Formula II:

[0040]

[0041] in

[0042] R1 is H, NH2 or OH;

[0043] R2 is H, NH2 or OH; and

[0044] R3 is H, NH2 or OH.

[0045] In one aspect, the invention provides a MOF or composition herein, wherein the linker comprises the formula of Table 1, 2, 3 or 4.

[0046] In the MOF or composition embodiments herein, the metal is a metal ion selected from the group consisting of: Li + 、Na + , K + , Rb + , Cs + 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ Sc 3+ Sc 2+ Sc + , Y 3+ , Y 2+ , Y + 、Ti 4+ 、Ti 3+ 、Ti 2+ 、Zr 4+ 、Zr 3+ 、Zr 2+ , Hf 4+ , Hf 3+ 、V 5+ 、V 4+ 、V 3+ 、V 2+ , Nb 5+ , Nb 4+ , Nb 3+ , Nb 2+ 、 5+ 、 4+ 、 3+ 、 2+ Cr 6+ Cr 5+ Cr 4+ Cr 3+ Cr 2 + Cr + ,Cr,Mo 6+ 、Mo 5+ 、Mo 4+ 、Mo 3+ 、Mo 2+ 、Mo + , Mo, W 6+ , W 5+ , W 4+ , W3+ 、W 2+ 、W + 、W、Mn 7+ 、Mn 6+ 、Mn 5+ 、Mn 4+ 、Mn 3+ 、Mn 2+ 、Mn + 、Re 7+ 、Re 6+ 、Re 5+ 、Re 4+ 、Re 3+ 、Re 2+ 、Re + 、Re、Fe 6+ 、F 4+ 、F 3+ 、F 2+ 、F + 、Fe、Ru 8+ 、Ru 7 + 、Ru 6+ 、Ru 4+ 、Ru 3+ 、Ru 2+ 、Os 8+ 、Os 7+ 、Os 6+ 、Os 5+ 、Os 4+ 、Os 3+ 、Os 2+ 、Os + 、Os、Co 5+ 、What 4+ 、What 3+ 、What 2+ 、What + 、Rh 6+ 、Rh 5+ 、Rh 4+ 、Rh 3+ 、Rh 2+ 、Rh + 、Ir 6+ 、Ir 5+ 、Ir 4+ 、Ir 3+ 、Ir 2+ 、Ir + ,Ir,Ni 3+ 、No 2+ 、No + 、Ni、Pd 6+ 、Pd 4 + 、Pd 2+ 、Pd +、Pd、Pt 6+ 、Pt 5+ 、Pt 4+ 、Pt 3+ 、Pt 2+ 、Pt + 、 Cu 4+ 、 Cu 3+ 、 Cu 2+ 、 Cu + 、Ag 3+ 、Ag 2+ 、Ag + 、I 5+ 、I 4+ 、I 3+ 、I 2+ 、I + 、Zn 2+ 、Zn + 、Zn、Cd 2+ 、Cd + 、Hg 4+ 、Hg 2+ 、Hg + 、B 3+ 、B 2+ 、B + 、Al 3+ 、Al 2+ 、Al + 、Ga 3+ 、Ga 2+ 、Ga + 、In 3+ 、In 2+ 、In1 + 、Tl 3+ 、Tl + 、Si 4+ 、Si 3+ 、Si 2+ 、Si + 、Ge 4+ 、Ge 3+ 、Ge 2+ 、Ge + 、Ge、Sn 4+ 、Sn 2+ 、Pb 4+ 、Pb 2+ 、As 5+ 、As 3+ 、As 2+ 、As + 、Sb 5+ 、Sb 3+ 、Bi 5+ 、Bi 3+ 、Te 6+ 、Te 5+ 、Te 4+、Te 2+ ,La 3+ ,La 2+ 、Ce 4+ 、Ce 3+ 、Ce 2+ , Pr 4+ , Pr 3+ , Pr 2+ 、Nd 3+ 、Nd 2+ 、Sm 3+ 、Sm 2+ 、Eu 3+ 、Eu 2+ , Gd 3+ , Gd 2+ , Gd + , Tb 4+ , Tb 3+ , Tb 2+ , Tb + 、Db 3+ 、Db 2+ 、Ho 3+ , Er 3+ 、Tm 4+ 、Tm 3+ 、Tm 2+ , Yb 3+ , Yb 2+ 、Lu 3+ and combinations thereof, including any complex containing the metals or metal ions listed above, and any corresponding metal salt counter anions.

[0047] In an embodiment, the invention provides a MOF or composition herein, wherein the metal is selected from aluminum, titanium, zirconium and hafnium.

[0048] In one aspect, the invention provides a method of preparing a MOF or composition herein comprising complexing a metal with a linker to form a MOF composition.

[0049] In one aspect, the invention provides a MOF or composition herein, comprising absorbing water in the composition.

[0050] The invention encompasses all combinations of specific embodiments detailed herein, as if every combination had been detailed sufficiently to be understood.

[0051] BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 : Type I organic linkers (angles between carboxylic acid groups of approximately 160°, such as linkers L1–L3) generate MOFs with cis-trans-shared AlO6 rod-shaped inorganic building blocks (also called secondary building units, SBUs).

[0053] Figure 2 : Type II organic linkers (angles between carboxylic acid groups of about 150°, such as linker L4) produce MOFs with 4 cis-4 trans-shared AlO6 rod-shaped inorganic building blocks (also called secondary building units, SBUs).

[0054] Figure 3 : Type III organic linkers (angles between carboxylic acid groups of about 120°, such as linkers L5-L9) generate MOFs with cis-trans-shared AlO6 rod-shaped inorganic building blocks (also called secondary building units, SBUs).

[0055] Figure 4a -g: Comparison of the framework structure and water arrangement in MOF-303 (left) and MOF-LA2-1 (right). (a) Linker 1H-pyrazole-3,5-dicarboxylic acid (H2PZDC) of MOF-303. (b) The alumina SBUs of both MOFs are composed of alternating cis-trans-corner-sharing AlO6 octahedra. (c) Linker (E)-5-(2-carboxylatovinyl)-1H-pyrazole-3-carboxylic acid (H2PZVDC) of MOF-LA2-1, where LA2-1 refers to the linker with two carbon atoms extending on one side. (d, e) Cross-sectional views of the pores showing the alignment of the pyrazolyl linkers so that their hydrophilic N(H) functional groups point toward each other, thus creating an alternating pattern of hydrophilic and hydrophobic pockets. The framework structure and water positions were obtained by a combination of X-ray diffraction analysis and DFT optimization. The hydrophilic pockets act as adsorption sites, shown with a loading of two water molecules per respective asymmetric unit [Al(OH)(PZDC)]2(d) and [Al(OH)(PZVDC)]2(e). (f,g) Snapshots of water structures from Monte Carlo simulations at full water loading (40 and 72 molecules per unit cell in f and g, respectively) are shown along the pores. The coordinate system is given for guidance. Al, blue octahedron; C and H, gray; N, green; O in the framework, pink; O in H2O, red.

[0056] Figure 5a -d: Experimental structure and water absorption analysis of MOF-LA2-1 compared with MOF-303. (a) Powder X-ray diffraction analysis using CuKα radiation. The main peaks are labeled according to the relevant crystallographic lattice planes. (b) Water absorption isotherm at 25 °C, P: water vapor pressure, P sat : saturated water vapor pressure. (c) Water desorption isobars at water vapor pressures of 1.27 and 1.70 kPa. The material was loaded at 30 °C and the corresponding water vapor before measurement. (d) 150 adsorption-desorption cycles at 1.70 kPa with temperature fluctuations from 30 to 45 °C.

[0057] Figure 6a -b: Water absorption isotherms of MOF-LA2-1 showing different linker configurations. (a) The most stable ZUS and ENT linker configurations used for simulations. Coordinate system is given for guidance. Al, blue octahedron; C and H, gray; N, green; O, pink. (b) Adsorption isotherms calculated using force field-based NpT-GEMC at 298K. Simulation and experimental data are shown as dashed and solid lines, respectively.

[0058] Figure 7 : Illustration of the four-part notation rule used to describe possible linker configurations in MOF-LA2-1. The μ2-OH functional groups are labeled with Arabic numerals to indicate symmetric equivalent groups.

[0059] Figure 8 Figure 3: Different linker configurations in MOF-LA2-1 optimized using DFT. The hydrophilic pocket of the MOF is shown for each configuration. MOF-LA2-1 configurations in which the pyrazole groups are present on the same side of the hydrophilic cavity (ZUS; two columns on the left) or on alternating sides of the hydrophilic cavity (ENT; two columns on the right), with cis- or trans-orientation of the vinyl group relative to the pyrazole ring. The electronic stabilities of each asymmetric unit [Al(OH)(PZVDC)]2 (ΔE) obtained from DFT for different MOF-LA2-1 structures are given in kJ·mol -1 Representation. Coordinate system is given for guidance. Al, blue octahedron; O, pink; N, green; C and H, grey.

[0060] Figure 9a -f: Major water binding sites in MOF-303 (a, b), MOF-LA2-1 in ZUS(w)-trans, trans configuration (c, d), and MOF-LA2-1 in ENT(w)-trans, cis configuration (e, f) at water loadings of 1 (a, c, e) and 2 (b, d, f) H2O molecules per asymmetric unit [Al(OH)(PZVDC)]2. Average binding energy of water molecules (ΔE ads,avg ) in kJ·mol -1 The hydrogen bond distance between heteroatoms is expressed as Shown are: Al, blue octahedron; C and H, gray; N, green; O in the framework, pink; O in H2O, red.

[0061] Description of Specific Embodiments of the Invention

[0062] Unless prohibited or otherwise indicated, in these descriptions and throughout the specification, the terms "a" and "an" mean one or more, and the term "or" means and / or. It should be understood that the embodiments and implementations described herein are for illustrative purposes only, and that various modifications or changes in view of these embodiments and implementations will occur to those skilled in the art, and will be included in the spirit and scope of this application and the scope of the appended claims. All publications, patents, and patent applications cited herein, including citations therein, are hereby incorporated by reference in their entirety for all purposes.

[0063] Linker L1 is an extended form of 1H-3,5-pyrazoledicarboxylic acid (linker of MOF-303) synthesized by a two-step procedure using Wittig reaction followed by hydrolysis. MOF-LA2 was obtained by solvothermal synthesis between aluminum salt (AlCl3·6H2O) and linker (L1) in aqueous NaOH solution or DMF / H2O mixture.

[0064] L1 synthesis scheme:

[0065]

[0066] MOF-LA2 synthesis scheme:

[0067]

[0068] MOF-LA2 adopts the same isoreticular structure as MOF-303, as shown in its powder X-ray diffraction pattern (PXRD). The water absorption isotherm curve shows a steep step at 26% RH, accompanied by a total water absorption capacity of 0.63 g / g. This is almost 1.5 times the water absorption capacity of MOF-303. Although shifted to the right compared to MOF-303, the water absorption step of MOF-LA2 is still close to the RH value corresponding to the conditions in the world's most arid regions.

[0069] The cycling experiments showed a negligible decrease in the overall water uptake capacity of MOF-LA2 after 29 additional cycles.

[0070] Table 1 shows several linker embodiments for the MOF-LA2 family with different substituents R. The introduction of hydrophilic groups such as -OH and -NH2 will shift the isotherm to even drier RH values, while the introduction of hydrophobic / neutral groups such as CH3 or halogens will shift the isotherm to higher RH. Other linker embodiments with core (X, Y, Z, I) variations are shown in Table 2.

[0071] Table 1: Examples of novel linkers of the MOF-LA2 family (R-variants).

[0072]

[0073] Table 2: Examples of novel linkers of the MOF-LA2 family (X, Y, Z, l-variants)

[0074]

[0075] All of these can be synthesized using the same method as L1. Similar to MOF-LA2, the experimental MOFs can be obtained by solvothermal synthesis in aqueous NaOH or DMA / H2O mixtures. Linkers L1-L3 (type I linkers) with inter-carboxyl angles very similar to those of L1 (about 160°) produce MOFs with the same network as MOF-303, showing cis-trans-shared AlO6 chain inorganic building blocks (also called secondary building units, SBUs; Figure 1 ). Linker L4 (type II linker) with an angle of about 150° produced a structure similar to CAU-23, showing 4 cis-4 trans-shared AlO6 chain inorganic building blocks ( Figure 2 Finally, linkers L5-L9 (type III linkers, approximately 120°) provided a MOF structure with the same network structure as CAU-10, showing cis-shared AlO6 chain inorganic building blocks ( Figure 3 ).

[0076] Embodiments of L1-L9 linkers that produce longer forms of the MOF-LA4 family are shown in Table 3. Representative examples of novel linkers for the MOF-LA5 family (n,m-variants) are shown in Table 4.

[0077] Table 3: Examples of novel linkers for the MOF-LA4 family (X, Y, Z, 1-variants).

[0078]

[0079] Table 4: Examples of novel linkers for the MOF-LA5 family (n,m-variants).

[0080]

[0081] Representative method for the synthesis of linkers L10-L18 (shown as L15), relying on the Knovenagel condensation between the corresponding bisaldehydes and malonic acid 13 .

[0082] L15 synthesis scheme:

[0083]

[0084] References

[0085] 1.Mekonnen,M.M.;Hoekstra,A.Y.Four Billion People Facing Severe WaterScarcity.Sci.Adv.2016,2,e1500323-e1500323。

[0086] 2.Gleick,P.H.Water in Crisis:A Guide to the World’s Fresh WaterResources;Oxford Univ.Press,1993。

[0087] 3.Fathieh,F.;Kalmutzki,M.J.;Kapustin,E.A.;Waller,P.J.;Yang,J.;Yaghi,O.M.Practical Water Production from Desert Air.Sci.Adv.2018,4,eaat3198。

[0088] 4.Hanikel,N.;Prévot,M.S.;Yaghi,O.M.MOF WaterHarvesters.Nat.Nanotechnol.2020,15,348-355。

[0089] 5.Kalmutzki,M.J.;Diercks,C.S.;Yaghi,O.M.Metal-Organic Frameworks forWater Harvesting from Air.Adv.Mater.2018,30,1704304。

[0090] 6.Byun,Y.;Je,S.H.;Talapaneni,S.N.;Coskun,A.Advances in Porous OrganicPolymers for Efficient Water Capture.Chem.Eur.J.2019,25,10262-10283。

[0091] 7. Hanikel, N.; Prévot, M. S.; Fathieh, F.; Kapustin, E. A.; Lyu, H.; Wang, H.; Diercks, N. J.; Glover, T. G.; Yaghi, O. M. Rapid Cycling and Exceptional Yield in a Metal-Organic Framework Water Harvester ACS Cent. Sci., 2019, 5, 1699 - 1706。

[0092] 8. Hanikel, N.; Pei, X.; Chheda, S.; Lyu, H.; Jeong, W.; Sauer, J.; Gagliardi, L.; Yaghi, O. M. Evolution of Water Structures in Metal-Organic Frameworks for Improved Atmospheric Water Harvesting. Science, 2021, 374, 454 - 459。

[0093] 9. Cadiau, A. et al., Design of Hydrophilic Metal Organic Framework Water Adsorbents for Heat Reallocation. Adv. Mater., 2015, 27, 4775 - 4780。

[0094] 10. Wahlgren, R. V. Atmospheric Water Vapour Processor Designs for Potable Water Production: A Review. Water Res. 2001, 35, 122。

[0095] 11. Xu, W., Yaghi, O. M. Metal-Organic Frameworks for Water Harvesting from Air, Anywhere, Anytime. ACS Cent. Sci., 2020, 6, 1348 - 1354。

[0096] 12. Burtch, NC; Jasuja, H.; Walton, KS Water Stability and Adsorption in Metal-Organic Frameworks. Chem. Rev. 2014, 114, 10575-10612.

[0097] 13. Sibi, Mukund P. et al., Preparation of Novel Monomers from Biomass, PCTInt.Appl.2016, 2016022943.

[0098] Example: MOF linker extension strategy for enhanced atmospheric water harvesting

[0099] Abstract: A linker-stretching strategy is proposed to generate metal-organic frameworks (MOFs) with excellent water-trapping properties. A collaborative design approach combining experimental and computational results leads to the development of MOF-LA2-1{[Al(OH)(PZVDC)](where PZVDC 2- (E)-5-(2-carboxyvinyl)-1H-pyrazole-3-carboxylate}) shows a 50% increase in water capacity compared to the state-of-the-art water-collecting material MOF-303. The function of this approach is to increase the pore volume without compromising the ability of the MOF to collect water in arid environments under long-term absorption and release cycles, as well as reducing the regeneration heat and temperature. Density functional theory calculations and Monte Carlo simulations give detailed insights into the framework structure, the interaction of water in its pores, and the resulting water absorption isotherms.

[0100] introduce

[0101] Water stress already affects about half of the world's population. 1,2 Given the availability of clean water in the atmosphere, porous hygroscopic adsorbents are being investigated for extracting water from the air. 3,4 Ideal water-harvesting materials should (i) absorb water at desired relative humidity (RH), including from desert air, (ii) exhibit step-like hygroscopic behavior to allow absorption and release of large amounts of water with minor perturbations in temperature or pressure, (iii) exhibit facile water release to reduce energy consumption and increase productivity, (iv) possess hydrothermal stability to enable long-term operation, and (v) be made from nontoxic, abundant components using environmentally friendly methods.

[0102] In this regard, metal-organic frameworks (MOFs) are promising materials because they can be designed and modified to achieve desired properties. 5-7 This has led to their successful implementation in atmospheric water harvesting. 8-14In particular, the discovery of MOF-303{[Al(OH)(PZDC)], in which PZDC 2- is 1H-pyrazole-3,5-dicarboxylate; Figure 4a} represents an important advancement in meeting the above-mentioned requirements for adsorbents. 11 Specifically, the aluminum oxide rod-like secondary structural unit (SBU, Figure 4b ) imparts hydrothermal stability to the framework and with the arranged PZDC 2- Together, the linkers create a pore lined by alternating hydrophilic-hydrophobic pockets. Single-crystal X-ray diffraction reveals how these pockets are ideally suited to bind the initial water molecules that seed the evolution of the overall water structure. 15

[0103] The challenge addressed in this study is how to maintain the alternating hydrophilic-hydrophobic pocket environment while increasing the water absorption capacity of the framework. In other words, how to increase the pore volume of MOF-303 without compromising its favorable water absorption properties. The usual strategy to increase the pore volume of aluminum MOFs made from rod-like SBUs is linker extension, which involves polycyclic aromatic linkers or the attachment of additional aromatic rings to the linkers. 16-19 However, these approaches produce hydrophobic, less porous or macroporous hydrolytically unstable aluminum frameworks. 16,19,22

[0104] Here, through an integrated experimental-computational approach, we identified and implemented a suitable linker extension strategy that involves appending a single vinyl group to PZDC 2- superior( Figure 4a The corresponding MOF (called MOF-LA2-1{[Al(OH)(PZVDC)], where PZVDC 2- is (E)-5-(2-carboxyvinyl)-1H-pyrazole-3-carboxylate; Figure 4c}) is isostructural with MOF-303, but with a 50% increase in pore volume and, therefore, increased water uptake. Although MOF-LA2-1 exhibits a slight shift to higher RH in its isotherm compared to MOF-303, it is still suitable for use in arid environments. In addition, this MOF offers significantly reduced regeneration temperature and enthalpy, as well as high stability in water adsorption-desorption cycles.

[0105] Results and discussion

[0106] At the outset of this study, we hypothesized that adding relatively compact but long groups to the hydrophilic H2PZDC linker used in MOF-303 would enhance its water uptake capacity while taking full advantage of its hydrophilic nature and its excellent stability ( Figure 4cIn particular, we were keen to preserve the arrangement of the pyrazole functional groups, which act as the primary adsorption sites and are key to their favourable water-harvesting properties ( Figure 4d ). 15 Density functional theory (DFT) calculations of periodic structures found to be consistent with the topology of MOF-303 indicated that the vinyl-appended variant would provide a favorable increase in pore volume (section S3.1). Therefore, the linker H2PZVDC featuring the vinyl extension of H2PZDC was synthesized by a two-step procedure applying a Wittig reaction on ethyl 5-formyl-1H-pyrazole-3-carboxylate followed by hydrolysis (section S2). MOF-LA2-1 was subsequently obtained by solvothermal synthesis using AlCl3·6H2O and H2PZVDC in a DMF / H2O (1:4) mixture at 120°C, as well as by a green synthesis procedure in H2O under reflux and stirring (section S2).

[0107] The obtained microcrystalline powders were first characterized by powder X-ray diffraction (PXRD) analysis. The significant 2θ shift of the corresponding PXRD reflections to lower values ​​compared to MOF-303 indicated the successful isoreticular extension of the parent framework ( Figure 5a ). In addition, these data together with scanning electron microscopy combined with energy dispersive X-ray spectroscopy confirmed the phase purity of the prepared samples (Section S4). In addition, we made great efforts to obtain single crystals suitable for single crystal X-ray diffraction (SCXRD) analysis of MOF-LA2-1, obtaining 10 × 10 × 30 μm 3 Although the synchrotron SCXRD data provide us with the unit cell parameters ( and β = 99.33(2)°) and insights into the SBU stereochemistry, we hypothesize that the relatively low crystallinity of these crystals is due to significant intrinsic positional disorder of the asymmetric linker in the crystal structure, thus limiting the overall SCXRD data quality and preventing us from obtaining the exact linker configuration in MOF-LA2-1.

[0108] We therefore utilized periodic DFT optimizations to probe the relative stability of different possible linker configurations in the MOF-LA2-1 structure under unit cell parameters extracted from the SCXRD data (Section S3.2). In this case, a total of 16 possible backbone configurations were considered, characterized by different positions and orientations of the pyrazole and vinyl groups in the hydrophilic cavity of the MOF. Typically, configurations in which the pyrazole functionalities were on the same side of the pocket (ZUS, from the German ‘zusammen’, to be together; as in Figure 4eThe ZUS configuration of MOF-LA2-1 is more stable than the configuration in which the pyrazole moieties are located on the opposite side of the pocket (ENT, from the German 'entgegen', opposite). We hypothesize that the pyrazole functionalities in the ZUS configuration of MOF-LA2-1 can form hydrogen bonds with each other, thus stabilizing the associated structural arrangement. This is further supported by the fact that in this configuration the pyrazole moieties are located in the same plane, whereas in the ENT configuration they are not. In general, a ZUS structure ( Figure 4e ) was identified as particularly stable, with the next most stable configuration at {[Al(OH)(PZVDC)]2 per asymmetric unit} being 27 kJ mol higher in energy. -1 (Section S3.2), therefore this ZUS structure is the most representative configuration of MOF-LA2-1.

[0109] As discussed previously, MOF-LA2-1 was derived from MOF-303 by adding vinyl groups to the H2PZDC linker molecule with the goal of enhancing its water uptake capacity while retaining the arrangement of pyrazole functional groups, which was identified as key to the water harvesting properties of MOF-303. After identifying the most stable backbone conformation, we computationally investigated the major water adsorption sites of MOF-LA2-1 in this arrangement and compared them with the corresponding sites in MOF-303 ( Figure 4d ,e). In fact, similar to the main water adsorption sites in MOF-303, water molecules are adsorbed on the sites formed by the linker pyrazole group and the μ2-OH group of the Al SBU. The first water molecule is bound by four hydrogen bonds. The N and NH groups of the linker form one hydrogen bond each, and the μ2-OH group of the aluminum SBU forms two hydrogen bonds. The second water molecule forms two hydrogen bonds (both The remaining N and NH groups each form a hydrogen bond ( Figure 4e These water adsorption sites are very similar to those observed in MOF-303 ( Figure 4d ), where the first water molecule adsorbs with comparable strength in MOF-303. The second water molecule adsorbs weakly relative to MOF-303 (Section S3.3), which contributes to the shift of the isotherm to slightly higher RH compared to MOF-303 (see below). Subsequent water molecules are expected to adsorb on the remaining μ2-OH groups of the Al SBU, and additional water molecules fill the pores by forming a hydrogen-bonding network, as previously observed in MOF-303 ( Figure 4f ,g). 15

[0110] Taking into account the insights gained from DFT calculations, we refined the structural model of MOF-LA2-1 in its most stable configuration with respect to the experimental PXRD data ( Figure 4e). The framework was modeled in the P21 / c space group (No. 14), and the final unit cell parameters were improved to and β = 98.6°, which are in good agreement with the SCXRD data.

[0111] Next, the thermal stability and porosity of MOF-LA2-1 were investigated using thermogravimetric analysis (TGA) and nitrogen adsorption analysis, respectively. TGA under both argon and air atmospheres revealed no significant weight loss below 300 °C. This indicates excellent stability required for thermal regeneration during water collection operations. Preliminary evaluation of the nitrogen adsorption isotherm of MOF-LA2-1 at 77 K revealed that the Brunauer-Emmett-Teller (BET) surface area and pore volume were 1892 m 2 g -1 and 0.67cm 3 g -1 , which is 1.4 times that of MOF-303. 15

[0112] The water-harvesting properties of MOF-LA2-1 were first probed by performing water adsorption measurements under isothermal conditions. Similar to the parent framework, the extended framework showed a pre-step in its isotherm, which is most likely related to the presence of a hydrophilic pocket formed by the pyrazole functional groups, thus forming a strong water adsorption site, as previously observed for MOF-303. 15 It is worth noting that at 26% RH, the water adsorption isotherm curve exhibits a steep step with a total water uptake of 0.64 gg -1 , 50% higher water capacity than MOF-303 ( Figure 5b ). Despite being shifted to slightly higher RH values ​​compared to MOF-303, the step position of MOF-LA2-1 is still suitable for water harvesting in the world’s most arid regions. 23,24 In addition, we performed water adsorption analysis at different temperatures and used these data to evaluate the isosteric heat of adsorption of water, Q, using the Clausius-Clapeyron relationship. st We found that the average Q of MOF-LA2-1 st The value is 50 kJ mol -1 , a total reduction of 4 kJ mol compared to the parent framework evaluated under similar conditions. -1 . 25 Considering the condensation heat of water (44 kJ mol at 25 °C) -1), which is similar to a 40% lower adsorption penalty than MOF-303. Importantly, we note that the favorable water absorption properties of MOF-LA2-1 are not compromised when the green reflux-based synthesis is used to prepare MOF-LA2-1.

[0113] Furthermore, the regeneration temperature of MOF-LA2-1 was probed by measuring isobaric desorption curves. These measurements were performed at water vapor pressures of 1.27 and 1.70 kPa (corresponding to 30% and 40% relative humidity at 30 °C, respectively) and demonstrated a significantly reduced water release temperature ( Figure 5c ), thus allowing a highly desirable operating desorption temperature of 45° C. Together with the significantly reduced isosteric heat of adsorption, these findings validate MOF-LA2-1 as an energy-efficient water-harvesting material for use in arid regions.

[0114] To examine the stability of MOF-LA2-1 under operating conditions, temperature swing adsorption-desorption cycles were performed at 1.70 kPa water vapor pressure ( Figure 5d ). This experiment showed that after 75 cycles, the water absorption working capacity decreased by 5%, and after 75 additional cycles, it decreased further by 1%, thus indicating that the capacity loss leveled off and the lifetime of MOF-LA2-1 was generally good.

[0115] We next investigated the dependence of water adsorption behavior on different linker configurations of MOF-LA2-1. To this end, force field-based Monte Carlo simulations in the Gibbs ensemble were used to calculate water adsorption isotherms at 298 K (Section S3.4). We focused these efforts on the most stable ZUS and ENT configurations, which serve as representative examples of different structural ensembles (Section S3.4). The simulated water adsorption isotherms of the two structural types showed significantly different curves ( Figure 6a -b): In good agreement with the measured adsorption isotherms, the ZUS configuration shows an initial water uptake of approximately five water molecules per unit cell consisting of four asymmetric units at 5% RH, and a sharp isotherm step at 30% RH. In contrast, the calculated isotherms of MOF-LA2-1 in the ENT configuration exhibit a flatter curve, which can be explained by the large number of water adsorption sites with different binding strengths to the pore walls. Based on the comparison with the experimental water adsorption isotherms, it can be concluded that the isotherms of the ZUS configuration are more representative of the experimental data, thus further supporting our structural model ( Figure 4e ).

[0116] In summary, we have demonstrated a linker "arm" extension strategy and used it to significantly enhance the water-harvesting properties of a state-of-the-art water-harvesting material, MOF-303. Importantly, it features a 50% increase in water uptake capacity and reduced operating energy requirements, while retaining the ability to capture water in arid regions and hydrothermal stability suitable for long-term uptake and release cycles. This approach is generalizable and particularly useful for commercially relevant aluminum-based MOFs.

[0117] Section S2: Synthesis process

[0118] Synthesis of (E)-5-(2-carboxyvinyl)-1H-pyrazole-3-carboxylic acid (H2PZVDC):

[0119]

[0120] Step 1: 13 To a 100 mL round bottom flask equipped with a stir bar under argon atmosphere was added 1 (1.5 g, 8.9 mmol, 1 eq) and anhydrous THF (50 mL). The mixture was cooled to -10 °C using an acetone / ice bath, and 2 (3.5 g, 10.5 mmol, 1.2 eq) was added portionwise. The reaction was allowed to warm to room temperature overnight. After concentrating the resulting solution under reduced pressure, the reaction mixture was purified by 1 HNMR analysis identified a mixture containing E and Z-isomers. Acetone / hexane (5 / 1) was used as the eluent (R f =0.1) The desired E-isomer 3 was separated by column chromatography. Yield: 1.3 g, 65%.

[0121] 1 H NMR (400MHz, CDCl3) δ10.93 (s, 1H), 7.67 (d, J = 16.0Hz, 1H), 7.04 (s, 1H), 6.48 ( d,J=16.0Hz,1H), 4.41(q,J=7.1Hz,2H), 3.81(s,3H), 1.41(t,J=7.1Hz,3H)ppm.

[0122] Step 2: A 100 mL round-bottom flask equipped with a stirring bar was charged with 3 (1.3 g, 5.8 mmol, 1 eq), MeOH (50 mL) and aqueous NaOH (20 mL, 1.5 M, 5 eq). The reaction was heated at 50 °C (oil bath temperature) until the starting material was consumed, monitored by TLC (2 h). The solution was concentrated under reduced pressure and 5 M HCl was added dropwise until pH = 2-3. The resulting precipitate was filtered off and washed thoroughly with H2O (4×10 mL) and MeOH (1×5 mL). After vacuum drying at 50 °C, the linker H2PZVDC was obtained as a white powder. Yield:

[0123] 1.0g,95%. 1 H NMR (500MHz, DMSO-d6) δ13.80-13.10(br.s,3H), 7.46(d,J=16.2Hz,1H), 7.17(s,1H), 6.53(d,J=16.1Hz,1H). 13 CNMR (126 MHz, DMSO-d6) ppm. δ 167.4, 161.4, 120.6, 108.4 ppm. HRMS (m / z): calculated for C7H5N2O4 [MH] - , 181.0255; found, 181.0255.

[0124] Solvothermal synthesis of MOF-LA2-1:

[0125]

[0126] In a 4 mL scintillation vial, the linker H2PZVDC (91.0 mg, 0.5 mmol, 1 eq) was dissolved in N,N-dimethylformamide (DMF) (0.6 mL) under ultrasound. An aqueous solution of AlCl3·6H2O (2.4 mL, 0.2 M, 1 eq) was added dropwise, and the resulting mixture was heated in an oven at 120°C for 24 h. After cooling to room temperature, the white precipitate was collected by centrifugation and washed with H2O (3×30 mL) and MeOH (3×30 mL). MOF-LA2-1 was heated under dynamic vacuum (~10 -3 The mixture was activated at room temperature for 12 hours at 400 mbar and then gradually heated to 120°C for 6.5 hours. Yield: 65.0 mg, 58%. Elemental analysis of MOF-LA2-1: 56 H 40 N 16 O 40 Al8 Calculated: C, 37.52; H, 2.25; N, 12.50%. Found: C, 36.78; H, 2.38; N, 11.95%.

[0127] Green synthesis MOF-LA2-1:

[0128]

[0129] In a 50 mL round-bottom flask, the linker H2PZVDC (364 mg, 2 mmol, 1 eq) and NaOH (160 mg, 4 mmol, 2 eq) were dissolved in deionized water (10 mL) under ultrasound. An aqueous solution of AlCl3·6H2O (6 mL, 0.33 M, 1 eq) was added dropwise for 10 minutes, and the reaction mixture was heated to 120 °C and refluxed for 2 hours. After cooling to room temperature, the white powder was collected by centrifugation and washed with deionized water (2 × 10 mL) and EtOH (3 × 10 mL). The white powder was dried in air overnight and then precipitated under dynamic vacuum (~10 -3 mbar) at 120°C for 12 hours. Yield: 301 mg, 66%. Elemental analysis of MOF-LA2-1: For C 56 H 40 N 16 O 40 Al8 Calculated: C, 37.52; H, 2.25; N, 12.50%. Found: C, 37.29; H, 2.43; N, 12.10%.

[0130] Section S3: Computational studies of MOF-LA2-1

[0131] Section S3.1: Initial predictions of pore volume and water adsorption properties

[0132] We first constructed the proposed MOF (MOF-LA2-1) from the mother MOF-303, in which the PZDC 2- The (1H-pyrazole-3,5-dicarboxylate) linker was connected by a PZVDC 2- Linker substitution. Without any prior knowledge of the experimental crystal structure of this MOF, we constructed a DFT-optimized structure of this MOF in which the contact angle between the alumina rods and the linker resembles that in MOF-303, where the pyrazole groups form an alternating pattern of hydrophilic-hydrophobic pockets. In this arrangement, vinyl extension allows for a greater than 30% increase in pore volume (0.598 cm) compared to the parent MOF. 3 ·g -1 0.452cm 3 ·g -1 ). Force-field-based Monte Carlo simulations in the NpT-Gibbs ensemble (see Section S1, Computational Methods for more details) were used to predict the water adsorption isotherm of MOF-LA2-1 at 298 K. The simulated adsorption isotherm showed a steep step at about 18% relative humidity with a total water uptake of 0.6 gg -1 , which increases to 1.5 times compared with the water absorption of MOF-303 predicted using the same procedure.

[0133] Section S3.2: Stability of different linker configurations in MOF-LA2-1

[0134] We used DFT calculations to investigate the relative stability of different possible linker configurations in the MOF-LA2-1 structure. A total of 16 different linker configurations ( Figure 8 ), differing in the position and orientation of the pyrazole and vinyl groups in the hydrophilic cavity of the MOF. We use a four-part labeling rule for these different linker configurations, which are described for classification purposes with the broad side of the pocket on the left and symmetrically equivalent μ2-OH groups (labeled 2; Figure 7 ) on the bottom left and right sides of the pocket. The first part of the nomenclature indicates whether the pyrazole groups from the opposing linkers in the hydrophilic pocket of the MOF are on the side of the cavity {denoted as ZUS (from the German 'zusammen', common)} or on the alternating sides {denoted as ENT (from the German 'entgegen', relative)}. The second part of the nomenclature indicates whether the pyrazole ring at the top of the cutaway view is on the wide side (denoted as w) or the narrow side (denoted as n) of the pocket. Finally, the geometry of the vinyl group relative to the corresponding pyrazole ring is reflected by the cis / trans notation starting from the linker at the top.

[0135] The relative stabilities of different linker configurations were evaluated using periodic DFT optimizations (PBE-D3 / 850 eV theoretical level, see Section S1 for computational methods for more details) of the backbone atoms of the empty MOFs constrained by experimentally determined (see Section S6 for more details) lattice parameters. In general, the ZUS linker configuration, in which the pyrazole groups are opposite each other in the hydrophilic cavity of the MOF, was found to be more stable than the ENT linker configuration, which can be attributed to potential hydrogen bonding stabilization between the opposing pyrazole groups in the ZUS linker configuration. In addition, the ZUS linker configuration in which the pyrazole groups are present on the wider side of the hydrophilic cavity {ZUS(w)} was found to be more stable than the linker configuration in which the pyrazole groups are present on the narrower side of the hydrophilic cavity {ZUS(n)}. This can be explained by potential steric constraints associated with the presence of two relatively large pyrazole groups on the narrow side of the pocket. In contrast to the ZUS linker configuration, in which the pyrazole groups in the hydrophilic MOF cavity are arranged in the same plane, the pyrazole groups in the hydrophilic cavity of the MOF with the ENT linker configuration are not arranged in the same plane. It was also found that the orientation of the vinyl group affects the relative stability of the MOF-LA2-1 structure. Generally, in the ZUS(w) configuration, the presence of the vinyl group cis-oriented relative to the pyrazole makes the MOF structure unstable. In contrast, the ZUS(n) configuration is stabilized by the presence of the vinyl group cis-oriented.

[0136] In summary, the ZUS(w)-trans, trans linker arrangement was found to be the most stable configuration of MOF-LA2-1. Four other linker configurations (i.e., ZUS(n)-cis, trans; ENT(w)-trans, cis; ZUS(w)-trans, cis; and ZUS(w)-cis, trans) were identified as energetically accessible linker configurations {ΔE values ​​of 27–29 kJ mol -1 Each asymmetric unit [Al(OH)(PZVDC)]2, i.e. about 4k at the MOF synthesis temperature of 373–393K B T}. The first four structures were used as representative structures to study the water adsorption behavior in MOF-LA2-1; no calculations were performed for ZUS(w)-cis,trans due to its similarity to ZUS(w)-trans,cis.

[0137] Section S3.3: Determination of the main water adsorption sites

[0138] MOF-LA2-1 is converted to PZDC by MOF-303 2- The addition of compact but long vinyl groups derived from MOF-303 to the linker was aimed at enhancing the water absorption capacity of MOF-303 while maintaining the arrangement of its pyrazole functional groups, which was identified as the key to the favorable water harvesting properties of MOF-303. To demonstrate this, we investigated the major water adsorption sites in the ZUS(w)-trans,trans and ENT(w)-trans,cis linker configurations of MOF-LA2-1, which serve as representative structures of ZUS and ENT configurations. In fact, similar to the major water adsorption sites previously identified in MOF-303 ( Figure 9a , b), in both linker configurations, water molecules are adsorbed in the sites formed by the pyrazole moiety and the μ2-OH group of the alumina rod.

[0139] In the ZUS(w)-trans,trans linker configuration, the first water molecule forms four hydrogen bonds with the backbone The NH and N groups of the two adjacent linkers each form one hydrogen bond, and the μ2-OH group of the alumina rod forms two hydrogen bonds (ΔE ads,avg =-84.6 kJ mol -1 ; Fig.9c ). The second water molecule is bonded to adsorption, the remaining NH and N groups of the adjacent pyrazole moieties each form a hydrogen bond (ΔE ads,avg =-57.7 kJ mol -1 ; Figure 9d). These water adsorption sites are similar to those observed in MOF-303, where the first H2O molecule adsorbs with comparable strength and the second H2O molecule adsorption is stronger than that in MOF-LA2-1 {ΔE ads,avg = -82.4 and -80.2 kJ mol -1 ; Figure 9a , b}. Subsequent water molecules are expected to adsorb on the remaining μ2-OH groups of the alumina rods, as previously observed for MOF-303. 1

[0140] In contrast, the H2O adsorption sites differ in the ENT(l)-trans, cis linker configuration, which can be explained by the spatial separation of the pyrazole groups. The first H2O molecule is bound to the backbone via four hydrogen bonds. adsorption, forming one hydrogen bond with the NH group, two hydrogen bonds with the μ2-OH group, and one hydrogen bond with the carboxylic acid group of the linker (ΔE ads,avr =-77.4 kJ mol -1 ; Fig.9e ). The second H2O molecule is bonded to Adsorption, the NH group of the alumina rod forms a hydrogen bond with the μ2-OH group of the alumina rod (ΔE ads,avr =-63.9 kJ mol -1 ; Figure 9f ). We note that in this linker configuration, the N group of the linker can adsorb subsequent water molecules, thus resulting in a greater number of sites favorable for H2O adsorption compared to MOF-303.

[0141] Section S3.4: Simulated water adsorption isotherms

[0142] We next probed the dependence of water adsorption behavior on different linker configurations of MOF-LA2-1. Force-field-based Monte Carlo (MC) simulations in an isobaric–isothermal (NpT) Gibbs ensemble were used to calculate water adsorption isotherms at 298 K. Considering the similarity of the main adsorption sites in MOF-LA2-1 and MOF-303 (Section S3.3), the simulation setup was chosen to be similar to previous studies that specifically predicted the water adsorption isotherm for MOF-303 (see Section S1 for more details on computational methods). 2The rigid backbone structure of MOF-LA2-1 was used for these calculations, which was optimized in the presence of 4 H2O molecules / unit cell (equivalent to 1 H2O / asymmetric unit) that were deleted prior to the MC simulations. This arrangement results in an enlarged hydrophilic cavity, thus explaining the structural flexibility of the MOF, which was previously shown to be important for obtaining a suitable initial water uptake in MOF-303. 2

[0143] Using the above procedure, water adsorption isotherms of MOF-LA2-1 in ZUS(w)-trans,trans; ZUS(n)-cis,trans; ZUS(w)-trans,cis and ENT(w)-trans,cis linker configurations were simulated. It is noteworthy that the ZUS and ENT linker configurations exhibit significantly different water adsorption behaviors. Consistent with the measured adsorption isotherms, both the ZUS(w)-trans,trans and ZUS(w)-trans,cis configurations (in which the pyrazole group is present on the wider side of the hydrophilic cavity) show an initial water uptake of approximately 5 water molecules per unit cell at 5% relative humidity (RH), as well as a sharp step in the isotherm jump at approximately 30% RH, which is slightly shifted from the experimental isotherm. We note that the two linker configurations differ only in the orientation of the vinyl group, and the similar adsorption behavior of the two linker configurations indicates that the orientation of the vinyl group (cis or trans) does not significantly affect the overall adsorption isotherm. On the other hand, the ZUS(n)-cis,trans linker configuration (where the pyrazole group is present on the narrow side of the hydrophilic cavity) shows no initial water uptake observed at <10% RH in the experimental isotherm, even though the framework structure for this linker configuration was optimized with 4 H2O molecules per unit cell. This is consistent with the observation during the DFT optimization that water molecules do not adsorb on the 'strong' adsorption sites, as observed for the other ZUS linker configurations. Instead, the adsorbed water molecules move out of the plane of the two pyrazole linkers into the MOF pores, thus not significantly enlarging the cavity upon water adsorption. This linker configuration shows a steep step in the isotherm at approximately 22% RH, thus showing a larger deviation from the experimental isotherm than the ZUS(w) configuration.

[0144] In contrast to the steep steps observed in the adsorption isotherms of the three investigated ZUS linker configurations, the ENT(w)-trans,cis linker configuration shows a more gradual increase in its water uptake. The pyrazole functional groups are more distributed in the hydrophilic cavities compared to the ZUS linker configuration, resulting in a greater number of energetically favorable adsorption sites in the framework. Considering the steep curves of the experimental isotherms, we conclude that the ENT linker configuration is not a suitable structural model, while the ZUS(w)-trans,trans and ZUS(w)-trans,cis linker configurations appear to be good representatives of the synthesized MOF-LA2-1.

[0145] Table S1: in ZUS(w)-trans, trans configuration {monoclinic, P21 / c (No. 14), The fractional atomic coordinates of MOF-LA2-1 with β = 98.6°} were obtained by Pawley refinement of the corresponding structural model with respect to the PXRD experimental data.

[0146]

[0147]

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Claims

1. A metal-organic framework (MOF) composition comprising a metal complexed with an organic linker of the formula: wherein X, Y, and Z are independently C(H), N(H), O, or S; R1-R5 are independently CH3, NH2, OH, halogen or H; m is an integer from 0 to 5; n is an integer from 1 to 5; l is an integer of 1 or 2; and b1 and b2 are independently a single bond or a double bond; and At least one b2 is a double bond.

2. The MOF composition according to claim 1, wherein the metal-organic framework (MOF) comprises a repeating core, wherein the core comprises secondary structural units linked to organic ligands (linkers), wherein the secondary structural unit comprises one or more metals or metal-containing complexes, and The secondary structural unit is connected to the organic ligand (linker) via the oxygen atom of the carboxylate group in the organic ligand.

3. The MOF composition according to claim 1, wherein: R1-R5 are H.

4. The MOF composition according to claim 1, wherein: 1, 2, 3, 4 or 5 of R1-R5 are CH3, NH2, OH or halogen, and the others are H.

5. The MOF composition according to claim 1, wherein: m is 0, 1 or 2, and n is 1, 2 or 3; or m is 0, 1 or 2, and n is 1 or 2.

6. The MOF composition according to claim 1, wherein: m is 0, and n is 1; m is 0, and n is 2; m is 1, and n is 1; m is 1, and n is 2; m is 1, and n is 3; m is 2, and n is 2; m is 2 and n is 3; or m is 3, and n is 3.

7. The MOF composition of claim 1, wherein l is 1.

8. The MOF composition according to claim 1, wherein: One, two or three of X, Y and Z are independently N(H), O or S.

9. The MOF composition according to claim 1, wherein: X and Y are N and NH, respectively, and Z is C.

10. The MOF composition according to any one of claims 1 to 9, wherein the linker has formula II: in R1 is H, NH2 or OH; R2 is H, NH2 or OH; and R3 is H, NH2 or OH.

11. The MOF composition of any one of claims 1 to 9, wherein the linker comprises the formula of Table 1, 2, 3 or 4.

12. The MOF composition according to any one of claims 1 to 9, wherein the metal is a metal ion selected from the group consisting of: Li + 、Na + , K + , Rb + , Cs + 、Be 2+ Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ Sc 3+ Sc 2+ Sc + , Y 3+ , Y 2+ , Y + 、Ti 4+ 、Ti 3+ 、Ti 2+ 、Zr 4+ 、Zr 3+ 、Zr 2+ , Hf 4+ , Hf 3+ 、V 5+ 、V 4+ 、V 3+ 、V 2+ , Nb 5+ , Nb 4+ , Nb 3+ , Nb 2+ 、 5+ 、 4+ 、 3+ 、 2+ Cr 6+ Cr 5 + Cr 4+ Cr 3+ Cr 2+ Cr + ,Cr,Mo 6+ 、Mo 5+ 、Mo 4+ 、Mo 3+ 、Mo 2+ 、Mo + , Mo, W 6+ , W 5+ , W 4+ , W 3+ , W 2+ , W + , W, Mn 7+ , Mn 6+ , Mn 5+ , Mn 4+ , Mn 3+ , Mn 2+ 、Mn + 、Re 7+ 、Re 6+ 、Re 5+ 、Re 4+ 、Re 3+ 、Re 2+ 、Re + 、Re、Fe 6+ 、F 4+ 、F 3+ 、F 2+ 、F + 、Fe、Ru 8+ 、Ru 7+ 、Ru 6+ 、Ru 4+ 、Ru 3+ 、Ru 2+ 、Os 8+ 、Os 7+ 、Os 6+ 、Os 5+ 、Os 4+ 、Os 3+ 、Os 2+ 、Os + 、Os、Co 5+ 、What 4+ 、What 3+ 、What 2+ 、What + 、Rh 6+ 、Rh 5+ 、Rh 4+ 、Rh 3+ 、Rh 2+ 、Rh + 、Ir 6+ 、Ir 5+ 、Ir 4+ 、Ir 3+ 、Ir 2+ 、Ir + ,Ir,Ni 3+ 、No 2+ 、No + 、Ni、Pd 6+ 、Pd 4+ 、Pd 2+ 、Pd + 、Pd、Pt 6+ 、Pt 5+ 、Pt 4+ 、Pt 3+ 、Pt 2+ 、Pt + 、C 4+ 、C 3+ 、C 2+ 、C + 、Ag 3+ 、Ag 2+ 、Ag + 、Have 5+ 、Have 4+ 、Have 3+ 、Have 2+ 、Have + 、Zn 2+ 、Zn + 、Zn、Cd 2+ ,CD + 、Hg 4+ 、Hg 2+ 、Hg + 、B 3+ 、B 2+ 、B + 、Al 3+ 、Al 2+ 、Al + 、Ga 3+ 、Ga 2+ 、Ga + ,In 3+ ,In 2+ ,In 1+ 、Tl 3+ 、Tl + ,And 4+ ,And 3+ ,And 2+ ,And + 、Ge 4+ 、Ge 3+ 、Ge 2+ 、Ge + 、Ge、Sn 4+ 、Sn 2 + 、Pb 4+ 、Pb 2+ 、Ace 5+ 、Ace 3+ 、Ace 2+ 、Ace + 、Sat 5+ 、Sat 3+ 、Bi 5+ 、Bi 3+ 、You 6+ 、You 5+ 、You 4+ 、You 2+ 、At 3+ 、At 2+ ,What 4+ ,What 3 + ,What 2+ 、Pr 4+ 、Pr 3+ , Pr 2+ 、Nd 3+ 、Nd 2+ 、Sm 3+ 、Sm 2+ 、Eu 3+ 、Eu 2+ , Gd 3+ , Gd 2+ , Gd + , Tb 4+ , Tb 3+ , Tb 2+ , Tb + 、Db 3 + 、Db 2+ 、Ho 3+ , Er 3+ 、Tm 4+ 、Tm 3+ 、Tm 2+ , Yb 3+ , Yb 2+ 、Lu 3+ and combinations thereof, including any complex containing the above-listed metals or metal ions, and any corresponding metal salt counter anions.

13. The MOF composition according to any one of claims 1 to 9, wherein the metal is selected from aluminum, titanium, zirconium and hafnium.

14. The method for preparing the MOF composition of claim 1, comprising complexing the metal with the linker to form the MOF composition.

15. A method of using the MOF composition of claim 1 comprising absorbing water in the composition.

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