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Crystallographic Visualization of Post-synthetic Nickel Clusters into Metal-Organic Framework Xiao-Ning Wang, Peng Zhang, Angelo Kirchon, Jialuo Li, WenMiao Chen, Yu-Meng Zhao, Bao Li, and Hong-Cai Zhou J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b06711 • Publication Date (Web): 09 Aug 2019 Downloaded from pubs.acs.org on August 10, 2019

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Journal of the American Chemical Society

Crystallographic Visualization of Post-synthetic Nickel Clusters into Metal-Organic Framework Xiao-Ning Wang,1,‡ Peng Zhang,2,‡ Angelo Kirchon,2 Jia-Luo Li,2 Wen-Miao Chen,2 Yu-Meng Zhao1, Bao Li,*,1and Hong-Cai Zhou*,2,3 1

Key laboratory of Material Chemistry for Energy Conversion and Storage, School of Chemistry and

Chemical

Engineering,

Huazhong

University

of

Science

and

Technology

Hubei Key Laboratory of Bioinorganic Chemistry & Materia Medica, Wuhan, Hubei 430074, People’s Republic of China. 2 Department of Chemistry, Texas A&M University, College Station, Texas 778433255, United States.

3

Department of Materials Science and Engineering, Texas A&M University,

College Station, Texas 77842, United States. ‡ These authors contribute equally

Supporting Information Placeholder ABSTRACT: Post-synthetic metalation (PSM) has been employed as a robust method for the postsynthetic modification of Metal-Organic Frameworks (MOFs). However, the lack of relevant information that can be obtained for the post-synthetically introduced metallic ions has hindered the development of PSM applications. Thanks to the advancement in single-crystal X-ray diffraction (SCXRD) technology, there have been a few recent examples in which successful post-synthetic introduction of single metal ions into MOFs occurred at the defined chelating sites. These works have provided useful explanations about the complicated host-guest chemistry involved in PSMs. On the other hand, there are only limited examples with crystallographic snapshots of the post-synthetic installation of metal clusters into the pores of MOFs using an ordinary SCXRD due to the loss of crystallinity of parent matrix during the PSM process. Herein, by the careful selection of starting materials and controlling the reaction conditions, we report the first crystallographic visualization of metal clusters inserted into Zr-based MOFs via PSM. The structural advantages of the parent Zr-MOF, which are inherited from the stable Zr6 cluster and triazole-containing dicarboxylate ligand, ensure both the preservation of high crystallinity and the presence of flexible coordination sites for PSM. Furthermore, PSM of metal clusters in a MOF pore space enhances stability of the final samples while ACS Paragon Plus Environment

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also imparting the functionality of a successful catalyst toward ethylene dimerization reaction. The related construction ideas and structural information detailed in this work can help lay the foundation for further advancements using the post-modification of MOFs as well as open new doors for the utilization of SCXRD technology in the field of MOFs.

Introduction The technology of single-crystal X-ray diffraction (SCXRD) is well known as one of the most powerful, credible, and popular characterization methods for probing structural information at the atomic and molecular level.1 However, the main limitation of this technology is its strict requirement for high quality, crystalline-state samples, which must be arranged in a regular atomic structure with a long-range ordered electron density distribution.2 Metal-Organic Frameworks (MOFs), as extremely robust materials, have shown fascinating applications in various fields due to their excellent structure-property relationships.3,4 The components or secondary building units (SBUs) of metal nodes and organic linkers in MOFs exhibits a very regular arrangement through coordination bonds, allowing for the detailed structure of MOFs to be characterized by SCXRD.5 Thanks to the assistance of SCXRD technology, the structural advantages of MOFs, such as diversity, adjustability, and tunability, have been well illustrated and utilized.6 However, due to the strict limitations of SCXRD technology, guest molecules either that reside within or that are post-introduced into the pores of the parent MOFs are very difficult to be crystallographically determined because of their incomplete occupancy and disordered arrangement.7 It is well known that MOFs could be excellent parental carriers towards the wide scope of guest substances, but the deficiency of explicit structural information has significantly limited the development of hostguest chemistry related to MOFs.8 Although it is possible to fit or analyze the host-guest interaction through neutron diffraction, high-precision XRD, or theoretical methods, these methods are difficult to generalize as conventional characterization routes because of the expensive requirements of equipment and professional theory.9 Therefore, exploring the host-guest chemistry of MOFs by virtue of standard SCXRD technology is still a great challenge. Over the last several years, developments of stable MOFs bring new opportunities to perform postsynthetic modification by means of covalent reaction on the organic linkers, metal cations/organic linkers exchange, capture and release, and many other means.10 For instance, the stable Zr-MOFs can serve as versatile platforms to allow the incorporation of terminal ligands, dicarboxylate linkers, metal cations, and metal−organic complexes onto the coordinative unsaturated Zr6 clusters.11 Most recently,

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post-synthetic metalation (PSM) has become a standardized method for the post-synthetic modification of MOF materials.12 PSM has helped us realize that MOF materials can serve as advanced heterogeneous catalysts for better gas adsorption or separation performances.13 In contrast to the strategy of metathesis onto metal nodes, anchoring metal ions to the framework of MOFs via their coordination vacancies and pore characteristics is more popular and suitable for most MOF materials.14 Previous studies have shown that the modification of nitrogen-based coordination sites plays an important role in the uniform and regular introduction of different metal ions in MOFs. It is well-known that metal ions can coordinate with nitrogen vacancies and attach onto the MOF skeleton, but there is an extremely small amount of evidence that clearly shows the true form of metal ions after attachment to the framework.15 By virtue of SCXRD technology, the limited results of the ordered metalation onto MOF skeletons have been reported and illustrated with explicit structural information of the host-guest chemistry occurring within the framework. Single-crystal X-ray diffraction is the straightforward and principal method for direct visualization of the three-dimensional structures before and after the structural transformation. Thus, single-crystal to single-crystal (SCSC) transformation is highly desirable to follow the structural changes. However, analysis of the extensive research associated with PSM of MOFs reveals that reported SCXRD information and current examples are not enough.16 The difficulties in achieving useful SCXRD information after PSM is usually caused by the low initial crystallinity of the parent MOFs, the inability to retain this crystallinity after the post-synthesis process, the inevitable disorder associated with the high symmetry of MOFs, or the fabrication of saturated coordination environments of the introduced metal ions.17 Consequently, single-crystal to single-crystal (SCSC) transformation is hard to occur and is of particular interest and importance. To resolve these issues, the existing work focuses on adding bi- or tri-dentate chelating sites onto the framework of MOFs and visualizing evidence of these postsynthetically introduced single metal ions via SCXRD.18 However, more challenging tasks, such as the achievement and detection of the PSM of metal clusters onto MOF skeleton via SCXRD technology, are seen as extremely valuable yet elusive. Differing from the facile pre-design strategy for chelating single metal ions onto MOF skeleton or the post-modification of nano-metal clusters into the pores of MOFs, how to effectively anchor entire metal clusters onto a MOF skeleton while monitoring with SCXRD technology is still a huge challenge.19 This work has remained elusive due to the difficulties of predesigning rational chelating sites for entire metal clusters and the inability to control the cluster formation in a defined and uniform manner. Although there are multiple difficulties and restrictions, more sophisticated work on this area is urgently needed to uncover the mysterious veil of PSM. ACS Paragon Plus Environment


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To truly observe the PSM of metal clusters onto the MOF skeleton by ordinary X-ray single-crystal diffractometer in our laboratory, a new Zr-MOF, [Zr6O4(OH)8(H2O)4(L)4]n ( HUST-1, HUST = Huazhong University of Science and Technology, H2L = 4,4’-(4-Amino-4H-1,2,4-triazole-3,5diyl)dibenzoic acid ), fabricated by the combination of zirconium ion and the specially designed Vshaped di-carboxylic acid containing triazole unit, is utilized for the following reasons. Firstly, thanks to the strong Zr-O bond and stable Zr6O cluster, Zr-MOF can exhibit extremely high kinetic stability and maintain high crystallinity suitable for diffraction studies, even under extreme conditions.20 Secondly, the vacant azole unit has excellent coordination abilities to form stable metal clusters. Thirdly, different from the normal ligands used in Zr-MOF, herein, the purpose of the utilization of V-shaped ligand is to eliminate the possible problem of disorder caused by the high symmetry of Zr-MOF parent.21 As a result, a combination of the selected components would fabricate the anticipated MOF, which would exhibit a rigid skeleton and reserve the flexible chelating coordination sites for PSM (Figure 1). In terms of these structural advantages described above, the fabricated Zr-MOF should be an excellent parent for PSM and might maintain the complete crystallinity to carry out the SCXRD studies. Fortunately, in accordance with our assumption, the definite PSM of different metal clusters onto MOF skeleton have been newly presented via SCXRD studies, which could fill the gap of the related research field. The related construction idea and structural information in this work have laid the foundation for further promoting the post-modification of MOFs, and opened a new door for the utilization of SCXRD technology on the field of MOFs.

Figure 1. The illustration of the structural advantages of the pre-designed Zr-MOF material.


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Results and Discussion Crystal Structure of HUST-1 The pristine crystal samples of HUST-1 were obtained via the reaction of ZrCl4 and H2L under solvothermal method, which were directly used for further characterization and PSM of other crystal samples. SCXRD studies for HUST-1 had been carried out on the normal diffraction equipment in our laboratory. Consistent with our assumption, HUST-1 crystallizes in low symmetric space group Pnnm since the utilization of V-shaped linkers would reduce the possibility of disorder caused by the high symmetry of MOF skeleton compared to other highly-symmetric Zr-MOFs. In HUST-1, each Zr ion adapts an eight-coordinated square-antiprismatic sphere that is occupied by eight oxygen atoms. Six Zr ions are inter-connected via μ3-O and μ3-OH units to form the eight-connected [Zr6(μ3-O)4(μ3OH)4(OH)4(H2O)4] inorganic brick, which is further capped by eight carboxyl groups of different ligands (Figure 2a). The adjacent symmetric Zr6 clusters are jointed by the deprotonated linkers to form the 3D distorted bcu network (Figure 6a). The bridging angle of the V-shaped linker is 152.56°, while the dihedral angles of the benzoate plane and central triazole are 17.77° and 33.64°, respectively. In addition, the dihedral of two carboxylate groups is 24.54°. A highly porous structure had been left in the final product (Figure S17), which had been occupied by a large amount of guest molecules. Calculated by PLATON program, the solvent accessible volume was determined to be 79.5 %. The central trizaole units disposed on the surface of the framework. Importantly, thanks to the V-shaped configuration of the di-carboxylate linker, the constructed Zr-MOF not only reserves the rigid skeleton along with an open porous structure, but it also pre-disposes flexible chelating coordination sites originating from two adjacent triazole units that belonged to the different di-carboxylate linkers (Figure 1). The dihedral and center-to-center distance of two triazole groups are 63.41° and 11.74 Å. Therefore, in terms of structural advantages, the rigid skeleton, strong coordination ability of vacant triazole unit, proper separation distances, broad flexible degree, and open porous skeleton endow HUST-1 with great potential as an excellent parent that could post-introduce metal clusters while reserving high crystallinity. Accordingly, these anticipated structural advantages of HUST-1 prompt us to explore the practical possibilities of whether the PSM of metal clusters into MOFs could be truly visualized by ordinary SCXRD technology.



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Figure 2. Crystal structures of HUST-1 (a), HUST-2 (b) and HUST-3 (c) determined by SCXRD. In order to fulfill the anticipated PSM of metal clusters in MOFs which could be monitored by SCXRD technology, one critical pre-requisite is the high stability of the MOF parent. Due to the strong Zr-O bond and stable Zr6 cluster, the pristine Zr-MOF exhibits high chemical stability in water and in different concentrations of HCl solution (Figure S1). Additionally, the thermal stability of Zr-MOF allows it to retain its structure up to 400 ℃ (Figure S23). However, the activated HUST-1 is unstable under a vacuum condition at 80 ℃ for ten hours, which is usually observed for Zr-MOFs with eightconnected Zr6 clusters.22 In spite of this, the reaction process of PSM takes place in the surrounding solvent, and the high stability of HUST-1 in water would ensure the occurrence of PSM reaction. Post-synthetic Metalation of Nickel Clusters


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Figure 3. The representative SCXRD images of crystal samples of HUST-1(a), HUST-2 (b) and HUST3(c) in four sets. Utilizing the triazole ligands to fabricate the versatile transitional metal clusters is one of the prevalent routines in coordination chemistry.23 MOFs have been proven to be an excellent parent matrix to load different guest molecules by virtue of their porous structure. Herein, HUST-1 inherits the advantages of triazole groups and MOFs, which exhibits the potential application in capturing guest molecules along with the reservation of high crystallinity. To present the crystallographic snapshot of PSM of metal clusters in MOFs, the pristine crystal samples of HUST-1 were tentatively immersed in different nickel salts (NiCl2, NiBr2, Ni(NO3)2, Ni(OAc)2, NiC2O4 ) under different conditions ( temperature, solvent, and reaction time ). After absorbing the nickel ions, the crystallinity of parent MOFs could be still retained validated by SCXRD and powder XRD. However, only the HUST-1 samples reacted with NiCl2 and NiBr2 in CH3CN at 80 ℃ exhibit the definite post-modified results, which could be validated by the



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diffraction images (Figure 3). From performing the SCXRD studies, it was realized that hepta-nuclear and tri-nuclear nickel clusters could be effectively introduced into the parent matrix of HUST-1 after the reaction at 80 ℃ for one week. To our best knowledge, the PSM of metal clusters in MOFs monitored via SCXRD technology have been successfully implemented, which has a very significant scientific value in understanding host-guest chemistry at an atomic level. When HUST-1 was immersed in the CH3CN solution containing NiCl2·6H2O salt for one week, a new crystal sample, HUST-2, was obtained. Thanks to the structural advantages of the pre-designed Zr-MOF, high crystallinity of the new crystal state was still preserved, even after the PSM process. Detailed information about the collection and refinement of crystal data had been listed in supporting information (Table S1). Compared to HUST-1, the diffraction images of HUST-2 exhibit higher resolution due to the incorporation of hepta-nuclear Ni clusters on the surface of the framework. The regular arrangement of post-modified hepta-nuclear clusters not only increases the electron density of the whole framework, but also enhances diffraction intensity of the crystal sample, compared to the low density of the original MOF with a large porous structure (Figure 3a, b). After integration and scaling of the whole data for HUST-2, there was no obvious change in cell parameters after PSM treatment, reflecting the rigid skeleton of the original framework. The main difference between HUST-1 and HUST-2 focuses on the flexible chelating coordination sites. In order to fit the kinetic requirement for stabilizing the postintroduced hepta-nuclear clusters, the adjacent triazole units must rotate to the proper positions and chelate onto the guest clusters. For HUST-2, the dihedral and the center-to-center distance of two triazole groups is 69.23° and 8.63 Å. Apart from this change, there are the other changes in the configuration of the whole linker. For example, the bridging angle of V-shaped linker is 142.37°; the dihedral angles of the benzoate plane and central triazole are 84.34° and 77.87°; the dihedral of two carboxylate groups is 36.32°. Comparably, there are slight differences occurring in the Zr6 inorganic brick. These variations adequately illustrate the important role of the disposed flexible chelating coordination sites in stabilizing the extra clusters. Through the presentation of SCXRD technology, the post-modified hepta-nuclear clusters exhibit the mirror-symmetric configuration. Ni1, Ni2, and Ni3 adopt the octahedral coordination sphere, whilst the coordination environment of Ni4 is a square pyramid. Ni3 atom is located in the central portion of the cluster, whose periphery is decorated by other six nickel ions via three μ3-OH and three μ3-Cl bridges. In the peripheral ring: Ni1 and Ni2 are connected via triazole unit, and μ3-OH and μ2-Cl bridges; Ni2 and Ni4, Ni1 and its symmetric Ni1A, are bound together by μ3-Cl and μ2-Cl bridges; the connection mode ACS Paragon Plus Environment

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between Ni4 and its symmetric Ni4A are μ3-Cl and μ2-Cl bridges. For Ni1 and Ni2, the vacant coordination sites are occupied by water molecules, whilst a chloride ion occupies the remanent site of Ni4 (Figure 5a). Compared to the original position of triazole in HUST-1, the obvious torsion has been presented in order to cater to the requirement of the post-modified cluster. Viewed from the packing mode, the post-modified clusters regularly distribute on the surface of the skeleton, and the specific porosity is still remained in the final framework (Figure 6b and Figure S18). Calculated by PLATON program, the solvent accessible volume in HUST-2 had been determined to be 62.6 %. In addition, the existence and ratio of nickel and chloride ions could be also validated by the comprehensive results of SEM (Figure 4b), XPS (Figure 4e, Figure S24 and S29) and ICP (Table S5).

Figure 4. Photo and SEM images of HUST-1(a), HUST-2 (b), HUST-3(c) and HUST-4 (d) along with the EDX mapping image of Zr, Ni, Cl and Br elements; XPS spectra of Ni element in HUST-2(e) and HUST-3(f). Differently, by substituting the metal salt with NiBr2·3H2O, tri-nuclear nickel clusters had been introduced onto the original framework to fabricate the new crystal sample of HUST-3. Compared to



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original HUST-1, the diffraction intensity and resolution of crystal sample HUST-3 were also enhanced, but weaker than HUST-2 (Figure 3c). The different nucleation numbers must be responsible for the difference in the presentation of diffraction patterns. The SCXRD studies for HUST-3 reveal that there are some minor changes in cell parameters, which is also ascribed to the torsion of bridged linkers. The dihedral and center-to-center distance of two triazole groups is 27.25° and 6.58 Å; the bridging angle of V-shaped linker is 138.75°; the dihedral angles of benzoate plane and central triazole are 65.76° and 65.95°; the dihedral of two carboxylate groups is 28.59°. In addition, the bridged linker exhibits the more bent configuration caused by the torsion in the process of dynamic PSM of clusters. The post-modified tri-nuclear cluster also adapts the mirror-symmetry due to the same spacial constraint, in which Ni1 and Ni2 adapt the square pyramid and octahedron coordination environments. Ni1 and Ni2 ions are bound together via triazole and μ3-OH, and two Ni1 and Ni2 ions are integrated to fabricate the typical trinuclear nickel cluster by the stabilization of two triazole groups (Figure 5b). Due to the weak coordination ability of bromide with nickel, the other vacant coordination sites of nickel ions are occupied by water molecules to form the complete configuration of tri-nuclear clusters. The postmodified clusters also regularly distribute on the surface of the skeleton viewed from the packing mode, and the certain porosity in the final framework is retained (Figure 6c and Figure S19). Calculated by

PLATON program, the solvent accessible volume in HUST-3 was determined to be 66.8 %. In addition, the existence and ratio of nickel and bromide ions could be also validated by the comprehensive results of SEM (Figure 4c), XPS (Figure 4f, Figure S24 and S30) and ICP (Table S5).


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Figure 5. The perspective view of the hepta-nuclear clusters in HUST-2 (a) and tri-nuclear clusters in HUST-3 (b). The phenomenon of the successful PSM of nickel clusters onto the skeleton of the original MOF could not be detected via SCXRD technology when the reaction temperature changed to room temperature. The crystallinity of samples after PSM could be also retained, but no definite post-modified metal ions could be observed, except for the slight changes of structural parameters of dicarboxyl linkers, as shown in Figure S20-22. Other characteristic methods with high diffraction intensity might be useful to give the definite states of post-modified nickel ions, but not the normal diffraction equipment. Therefore, the sample loaded with nickel ions had been termed as HUST-4, in order to distinguish HUST-2 and HUST-3. The dihedral and center-to-center distance of two triazole groups is 57.23° and 11.62 Å; the bridging angle of V-shaped linker is 148.17°; the dihedral angles of benzoate plane and central triazole are 29.05° and 30.65°; the dihedral of two carboxylate groups is 23.88°. There are lots of ambiguous diffraction densities residue in the cavities of HUST-4, which could not be fixed as the definite states. The low reaction temperature could not supply enough energy surrounding the energy barrier for fabricating the related clusters and result in the low load amount of nickel ions in HUST-4 compared to HUST-2 and HUST-3.



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Comprehensively, in order to achieve the desired goal of crystallographic snapshot of PSM of metal clusters into the porosity of MOFs, the parent MOF scaffold must exhibit the following specific characteristics: A rigid skeleton for the reservation of high crystallinity during PSM process; Uniform distribution of a flexible chelating environment to adapt the spatial requirements for the formation of variable metal clusters; Existence of vacant coordination positions with strong coordination abilities to accept the post-synthetic metal ions. Herein, the constructed Zr-MOF possesses the composite advantages and truly exhibits the single-crystal to single-crystal transformation triggered by the PSM of metal clusters in the porosity of MOF, which imparts a unique reference for post-modifying phasechange materials.

Figure 6. The perspective view of the packing mode and topological structure of HUST-1(a), HUST-2 (b) and HUST-3(c) along b-axis direction. The rectangular, purple ball, hexagonal and triangle represent the Zr6 cluster, di-carboxylate ligand, hepta-nuclear and tri-nuclear clusters, respectively. The characteristic porosities in the parent MOF and derived MOFs were also significantly altered after the inclusion of post-modified metal clusters, proven by the N2 sorption isotherms at 77 K. HUST-1 exhibits a typical type IV isotherm morphology, with a N2 uptake of 13.07 cm3 g−1 and a Langmuir Surface Area of 48.22 m2 g−1. The low adsorption capacity indicates the collapse of framework in HUST-1, in consistent with the other similar Zr-MOFs consisted of 8-connected cluster.22 Comparably, after the introduction of hepta-nuclear nickel cluster into HUST-1, HUST-2 exhibits a typical type I isotherm morphology, with a N2 uptake of 100.01 cm3 g−1 and a Langmuir Surface Area of 289.69 m2 g−1. The larger parameters illustrate the more stable porous framework in HUST-2, and further manifest the


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important role of the PSM metal clusters to the reservation of porous framework. However, the N2 adsorption isotherm of HUST-3 gives the slightly parameters compared to the ones of HUST-1, which might be caused by the unstable Ni3 cluster. Therefore, all of the comparable adsorption phenomenons adequately emphasize the important role of the post-modified metal clusters to stabilize the porous framework. Cooperative Catalytic Performances of Post-modified MOFs PSM of metal clusters not only provides an efficient synthetic route to obtain the post-modified materials but also facilitates the new functionalization into MOFs. For example, by virtue of the intrinsic catalytic activities of installed metal species and the high stability of Zr-MOF framework, the obtained MOFs can be explored as heterogeneous catalysts towards specific reactions. Herein, we investigated the catalytic properties of Ni-containing MOFs in ethylene dimerization reactions. The reactions were carried out in the stainless-steel batch reactor under 40 bar of ethylene in toluene at 25 °C, and diethyl aluminum chloride (Et2AlCl) was adopted as the activator (Table 1). In every experiment, the amount of catalyst was fixed to 5 mg, and the real molar amount of Ni calculated from ICP was shown in the bracket since the Ni content is different in each catalyst. As the blank controls, we first examined the ethylene dimerization under the activator Et2AlCl alone and with the presence of the parent MOF HUST-1 (entries 1 and 2). Both experiments showed no activity, further proving that the reaction occurs on the installed Ni species. Furthermore, UiO-67-Ni (Zr6O4(OH)4(bpydc)6(NiBr2)6 (bpydc = 2,2′-bipyridine-5,5′-dicarboxylic acid) as the reference (entry 3) had been utilized, since the presented framework bearing catalytic active Ni-bipyridine moiety has been widely accepted as an effective MOFbased catalyst for ethylene dimerization.24 Compared to UiO-67-Ni, the series of HUST MOFs showed higher activity and better 1-butene selectivity (entries 4-6) due to their relatively larger pores and facilitated mass transport inside the pores. Notably, HUST-3 shows the best activity for ethylene dimerization, even if its Ni content is not the highest among the three catalysts after PSM treatment (entry 5). The intrinsic activity of HUST-3 reached 4300 h-1 for butene production based on Ni, which is six times higher than that of HUST-2 and three times higher than that of HUST-4. Considering their similar parameters of unit cells (Table S1), the coordination environments of Ni ion showed significant impact on their catalytic activities. Visualized from the results of SCXRD, much more open sites had been exposed on the surface of channels in terms of the coordinatively unsaturated nickel ions fixed in the framework of HUST-3. The more regular arrangement of nickel ion of the hepta-nuclear cluster in HUST-2 lead to the saturate coordination environment and less open metal sites, which is the main reason that the lowest catalytic performance had been presented compared to HUST-3 and HUST-4. ACS Paragon Plus Environment


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Although the real nickel state could not be fixed, the separated nickel centers and open metal sites in HUST-4 should be responsible for the higher catalytic performance than the ordered and saturated nickel ions in HUST-2.11 In addition, although HUST-3 has no nitrogen adsorption after thermal activation, the framework is highly robust when operated in the liquid phase, and the active sites within the pores remain accessible. The catalyst can keep its high activity for at least three runs in the recycle experiments without significant loss of Ni content and crystallinity, as confirmed by ICP and XRD (Table S5 and Figure S6). Table 1. Ethylene Dimerization Catalyzed by Ni-Containing Catalysts a Catalyst, Et2AlCl 25 oC, 40 bar

Catalyst b

Entry

( h-1 )

Selectivity (%) 1-

2-

C6= +

C4=

C4=

C8=

1

none

0

0

0

0

2

HUST-1 (0 μmol)

0

0

0

0

3

UiO-67-Ni (5.3 μmol)

520 ± 30

59.0

29.8

11.2

4

HUST-2 (10.7 μmol)

740 ± 50

72.0

17.4

10.6

4570 ± 230

77.0

11.9

11.1

1550 ± 100

77.6

14.8

7.6

HUST-3

5 6 a

C4= Intrinsic Activity c

(5.1μmol) HUST-4 (2.6 μmol)

Reactions were carried out in the batch reactor under 40 bar of ethylene at 25 °C using toluene as the solvent, 5 mg of

catalyst, and 1.5 mmol Et2AlCl as the activator. b

Ni contents were calculated from the ICP data.

c

Calculated based on the moles of butenes generated and the Ni content. Standard deviations were calculated based on

three runs.

Conclusion In conclusion, by the rational design of the initial components, a matrix Zr-MOF had been fabricated, which is the excellent carrier that could effectively immobilize the dissociative metal ions into its framework as the form of metal clusters. More importantly, the definite configuration of the PSM metal clusters could be detected via the normal SCXRD technology. By the utilization of the different metal salts, the hepta-nuclear and tri-nuclear states captured in the designed Zr-MOF had been presented, ACS Paragon Plus Environment

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which firstly illustrates the feasibility that the detailed configuration of PSM metal clusters could be emerged via the normal SCXRD technology. The presented results manifest HUST-1 not only would be of the excellent platform to observe the structural configuration of the post-introduced substance, but also illustrate the potential application as “Crystal Sponge” applicable to inorganic materials.25 Additionally, the successful examples illustrate the key role of the synthesis strategies to expand the functional scopes and application categories of MOFs. Therefore, this work gives a fresh insights into the fabrication of tailored MOF-based platform for sophisticated applications, especially for the structural determination of post-introduced guest molecules. ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: The detailed experimental methods, crystal data, theoretical calculation methods and results (PDF) AUTHOR INFORMATION Corresponding Author * E-mail: [email protected] (B.L.). * E-mail: [email protected] (H.-C. Z.). ORCID Bao Li: 0000-0003-1154-6423 Angelo Kirchon: 0000-0003-1082-9739 Hong-Cai Zhou: 0000-0002-9029-3788 Notes The authors declare no competing financial interests. ACKNOWLEDGMENTS This work was supported by the financial supports of National Science Foundation of China ( 21471062 ), the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center (EFRC) funded by the U.S. Department of Energy (DOE), Office of Science, and Office of Basic Energy Sciences (DESC0001015), Office of Fossil Energy, the National Energy Technology Laboratory (DE-FE0026472), and the Robert A. Welch Foundation through a Welch Endowed Chair to HJZ (A0030), the Fundamental Research Funds for the Central Universities (2019kfyRCPY071, 2019kfyXKJC009). ACS Paragon Plus Environment


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