Skip to main content
NCBI home page
ACS AuthorChoice logoLink to ACS AuthorChoice
. 2021 Jan 13;143(3):1485–1492. doi: 10.1021/jacs.0c11247

Pore Engineering for One-Step Ethylene Purification from a Three-Component Hydrocarbon Mixture

Baoyong Zhu ∥, Jian-Wei Cao ‡, Soumya Mukherjee §, Tony Pham ⊥, Tao Zhang ‡, Teng Wang ‡, Xue Jiang ‡, Katherine A Forrest ⊥, Michael J Zaworotko §,*, Kai-Jie Chen ‡,*
PMCID: PMC8297724  PMID: 33439004

Abstract

graphic file with name ja0c11247_0006.jpg

Ethylene production from C2 hydrocarbon mixtures through one separation step is desirable but challenging because of the similar size and physical properties of acetylene, ethylene, and ethane. Herein, we report three new isostructural porous coordination networks (NPU-1, NPU-2, NPU-3; NPU represents Northwestern Polytechnical University) that are sustained by 9-connected nodes based upon a hexanuclear metal cluster of composition [Mn6(μ3-O)2(CH3COO)3]6+. NPU-1/2/3 exhibit a dual cage structure that was systematically fine-tuned in terms of cage size to realize selective adsorption of C2H2 and C2H6 over C2H4. Dynamic breakthrough experiments demonstrated that NPU-1 produces ethylene in >99.9% purity from a three-component gas mixture (1:1:1 C2H2/C2H4/C2H6). Molecular modeling studies revealed that the dual adsorption preference for C2H2 and C2H6 over C2H4 originates from (a) strong hydrogen-bonding interactions between electronegative carboxylate O atoms and C2H2 molecules in one cage and (b) multiple non-covalent interactions between the organic linkers of the host network and C2H6 molecules in the second cage.

Introduction

Ethylene (C2H4) is one of the most important industrial products, with production levels of >150 million tons in 2016.1 The energy footprint needed to purify ethylene and propylene (C3H6), another high-volume product, means that they collectively account for ca. 0.3% of global energy.2 Currently, C2H4 is mainly produced by steam-cracking reaction of carbon-included feedstocks, and high-purity ethylene is afforded by energy-intensive separation processes of downstream C2 hydrocarbon gas mixtures.3 Acetylene (C2H2) is first removed by catalytic hydrogenation using noble metal catalysts at high temperature and pressure, whereas ethane is later separated from C2H4 by cryogenic distillation. A transition to a more energy-efficient separation technology with a much lower energy footprint and simplified separation process (e.g., simultaneous removal of C2H2 and C2H6 in one step) for ethylene production would be of societal relevance.

Physisorption-based separation processes hold the promise for greatly reducing energy consumption of gas separation, thanks to the low regeneration temperature and fast sorption kinetics typical of physisorbents.4 Porous coordination networks based upon metal–organic materials (MOMs),5 also known as metal–organic frameworks (MOFs)6,7 and porous coordination polymers (PCPs),8 have emerged as promising C2 light hydrocarbon physisorbents due to their amenability to exquisite control of pore shape and chemistry through reticular chemistry and crystal engineering strategies.9,10 In this context, recent progress has been made with respect to binary separations such as C2H2/C2H4 and C2H6/C2H4.11−32,32 Simultaneous removal of both C2H2 and C2H6 in a single step would simplify the purification of C2H4 but remains a challenge for a single physisorbent. This is because the quadrupole moment and kinetic diameter for C2H4 (1.5 × 10–26 esu cm2 and 4.1 Å) sit between those of C2H2 (7.2 × 10–26 esu cm2 and 3.3 Å) and C2H6 (0.65 × 10–26 esu cm2 and 4.4 Å). These physicochemical properties exacerbate the challenge for one-step C2H4 production from C2H2 and C2H6 by either molecular sieving or thermodynamic selectivity. Thus far, we are aware of only three literature reports of C2H4 production from a C2H2–C2H4–C2H6 mixture in a one-step process. In 2018,33 simultaneous trapping of C2H2 and C2H6 was realized by the MOF TJT-100 thanks to the hierarchy of weak sorbent–sorbate interactions. In 2019,34 we introduced the concept of synergistic sorbent separation technology (SSST) to enable high-purity ethylene production from the ternary mixture (C2H2–C2H4–C2H6) and quaternary mixture (C2H2–C2H4–C2H6–CO2) by using tandem packing of three MOMs in a fixed-bed sorbent. In SSST, three benchmark sorbents (SIFSIX-3-Ni, TIFSIX-2-Cu-i, and Zn-atz-ipa) were selected for CO2, C2H2, and C2H6 removal, respectively. Most recently,35 a Th-azole network (Azole-Th-1) enabled selective adsorption of ethane and acetylene over ethylene. The discovery of new physisorbents that enable selective adsorption of C2H2 and C2H6 over C2H4 is timely not just to address the practical utility of such sorbents but also to advance our understanding of C2H2, C2H4, and C2H6 binding sites in porous materials.

In this contribution, we introduce the new hexanuclear Mn cluster [Mn6(μ3-O)2(CH3COO)3]6+ and its use as a building block for three isostructural 9-connected (9-c) MOMs with varying pore size. The hexanuclear metal cluster can be viewed as a fusion of two well-known trinuclear metal clusters bridged by three acetate anions. The Mn6 cluster reported herein has the potential to sustain 12-c networks, whereas the trinuclear parent typically serves as a 3-c, 6-c, or 9-c node (Scheme 1).36−41 The linking of the Mn6 cluster by rigid dicarboxylate linker ligands (BDC = 1,4-benzenedicarboxylate; NPDC = naphthalene-2,6-dicarboxylate; BPDC = biphenyl-4,4′-dicarboxylate) and the 3-connected pyridyl-based tritopic ligand 2,4,6-tris(4-pyridyl)pyridine (Tripp) afforded three isostructural MOMs (NPU-1, NPU-2, and NPU-3; NPU = Northwestern Polytechnical University) with tunable pore size and pore chemistry. We report herein the C2 sorption and separation properties of these new sorbents.

Scheme 1. M3(μ3-O) Metal Clusters Are Well Studied and Have Previously Been Used to Construct 3-, 6-, or 9-Connected Porous Coordination Networks (Left); Augmented 9-Connected Networks Are Reported Herein from a New Mn6(μ3-O)2 Cluster (Right).

Scheme 1

Open in a new tab

Results and Discussion

Single crystals of NPU-1, NPU-2, and NPU-3 were harvested following solvothermal reaction of manganese acetate tetrahydrate, Tripp, and a dicarboxylic acid ligand (H2BDC, H2NPDC, or H2BPDC) in N,N-dimethylacetamide (DMA) at 373 K. Single-crystal structure analysis revealed that the three materials are isostructural 3D networks based on the aforementioned hexanuclear Mn6 cluster. The novel Mn6 cluster can be regarded as the result of fusion of two M3(μ3-O) clusters through bridging acetate anions. Each manganese cation adopts an octahedral geometry through coordination with two oxygen atoms from two dicarboxylate ligands, two oxygen atoms from acetate anions, one μ3-O atom, and one nitrogen atom from Tripp (Supplementary Figure 1). Overall charge neutrality of these networks requires mixed-valence MnIII and MnII cations, which is supported by X-ray photoelectron spectroscopy (XPS) analysis (Supplementary Figure 2) and suggests electron delocalization. Unsuccessful ion-exchange experiments with charged dye molecules were conducted upon NPU-1 and NPU-3, indicating an absence of extra-framework counterions (Supplementary Figure 3). Such dye exchange experiments have been utilized by others to verify the charge state of host coordination networks.45 The general formula for NPU-1/2/3 is Mn5IIMnIII(μ3-O)2(CH3COO)3(Tripp)2(L)3 (L = BDC2–/NPDC2–/BPDC2– for NPU-1/2/3, respectively).

M3(μ3-O) clusters are normally connected by three, six, or nine organic linker ligands, but the Mn6 cluster in NPU-1/2/3 is bonded to 12 linker ligands (six dicarboxylate ligands and six Tripp ligands). The potential for rare 12-c nodes exists,5,42−44 but pairs of Tripp ligands serve as parallel 3-c nodes that connect to the same adjacent Mn6 cluster. Therefore, the Mn6 cluster should be viewed as a 9-c node, and NPU-1/2/3 are classified as 3,9-connected networks with pacs topology46 (Supplementary Figure 4). A similar “double cross-linking” situation occurred in the metal–organic polyhedron of formula [Cu2(bdc)2]12 (bdc = 1,3-benzenedicarboxylate). In this case, the 24 accessible connection points can serve as 6-c or 24-c nodes to build augmented pcu or rht networks.47,48 Notably, there are dual cages (A and B) in NPU-1/2/3 (Figure 1). Cage A has a trigonal bipyramidal shape, as it is surrounded by five metal clusters, six dicarboxylate ligands, and six Tripp ligands. Whereas the equatorial dimension of Cage A is consistent in NPU-1/2/3 (0.79 nm after subtracting the van der Waals radii of the nearest atoms), the axial dimension increases with the length of the dicarboxylate linker ligands (1.26, 1.77, and 2.24 nm for NPU-1/2/3, respectively). Cage B exhibits a distorted triangular prismatic shape, as it is formed from six adjacent Mn6 clusters, six dicarboxylate ligands, and four parallel Tripp ligands. The axial dimension in cage B varies from 0.38 to 0.66 to 0.91 nm for NPU-1/2/3, respectively. Each cage A is connected to six cage B’s in a face-shared manner, and vice versa. The triangular interconnecting pore windows between these cages, which are surrounded by one Tripp ligand and two carboxylate ligands, exhibit aperture sizes of 0.48 nm for NPU-1, 0.6 nm for NPU-2, and 0.78 nm for NPU-3. As revealed below, the dual cage nature of NPU-1/2/3 is crucial to their selective adsorption of C2H2 and C2H6 over C2H4. The porosity of NPU-1, NPU-2, and NPU-3 as calculated by PLATON49 was found to be 50.8%, 56.8%, and 62.1%, respectively.

Figure 1.

Figure 1

Open in a new tab

NPU-1/2/3 are isostructural coordination networks that are based upon assembly of Mn6 clusters, Tripp ligands, and different dicarboxylate linker ligands. The three-dimensional pore structures comprise two distinct cages.

Bulk purity of NPU-1/2/3 was confirmed by powder X-ray diffraction (PXRD, Figure 2a and Supplementary Figures 6–8). Thermogravimetric analysis (TGA) of as-synthesized and CH2Cl2-exchanged samples revealed that the DMA solvent in the as-synthesized phase can be fully exchanged with CH2Cl2 and that NPU-1/2/3 are thermally stable until 573 K (Supplementary Figures 9–11). N2 sorption experiments were conducted at 77 K to establish permanent microporosity, and NPU-1/2/3 each exhibited reversible type-I adsorption isotherms. By assuming pore filling by liquid N2 at 77 K and 100 kPa, the pore volumes calculated from N2 uptake at 100 kPa are 0.47 for NPU-1, 0.66 for NPU-2, and 0.77 cm3 g–1 for NPU-3. These values match well with the values of 0.53 for NPU-1, 0.68 for NPU-2, and 0.84 cm3 g–1 for NPU-3 calculated from the respective crystal structures. These findings are consistent with the absence of counterions in the pore channels of NPU-1/2/3. Langmuir and Brunauer–Emmett–Teller (BET) surface areas were calculated to be 1557 and 1396, 1844 and 1580, and 2133 and 1834 m2 g–1 for NPU-1/2/3, respectively. Horvath–Kawazoe (pore geometry: cylinder) and NLDFT model (pore geometry: slit)-based pore size distribution analyses were conducted upon the corresponding N2 sorption isotherms (Figure 2c and Supplementary Figure 12). A gradually increasing trend in pore size distribution was noticed upon increasing the length of the dicarboxylate ligands (peak position: 0.74 nm in NPU-1, 1.05 nm in NPU-2, and 1.22 nm in NPU-3), in agreement with the crystal structures.

Figure 2.

Figure 2

Open in a new tab

PXRD patterns and sorption data for NPU-1, NPU-2, and NPU-3. (a) Experimental and calculated PXRD patterns. (b) N2 sorption isotherms at 77 K. (c) Calculated pore-size distribution from 77 K N2 sorption data. (d) C2 gas sorption isotherms of NPU-1, (e) NPU-2, and (f) NPU-3 at 298 K. (g) IAST selectivity of C2H6/C2H4 (1:1 ratio) and C2H2/C2H4 (1:1 ratio) at 298 K and 100 kPa. (h) C2 gas adsorption enthalpies at low loading. (i) Optical microscope image of NPU-1 crystals.

The microporosity of NPU-1/2/3 prompted us to collect pure gas sorption isotherms at 273 and 298 K for C2H2, C2H4, and C2H6 up to 100 kPa (Figure 2d–f, Supplementary Figures 13–15). NPU-1 is the sorbent with the smallest pore size and exhibited the largest adsorption capacity for C2H2, C2H4, and C2H6, followed by NPU-2 (intermediate pore size) and NPU-3 (largest pore size). That the gas uptake at ambient temperatures was observed to increase with decreasing pore size is expected for microporous (<2 nm pores) materials.50 Notably, at 298 K, NPU-1 was found to exhibit higher uptakes of C2H2 (5.1 mmol g–1) and C2H6 (4.5 mmol g–1) than C2H4 (4.2 mmol g–1) at 100 kPa. This trend is maintained at relatively low pressures (0–30 kPa), implying selective adsorption of C2H2 and C2H6 vs C2H4 across the range of loading in NPU-1. Despite lower C2H2 (4.03 and 2.58 mmol g–1, respectively), C2H4 (3.45 and 2.22 mmol g–1), and C2H6 uptakes (4.44 and 3.36 mmol g–1) for NPU-2 and NPU-3 at 298 K and 100 kPa vs NPU-1, a similar phenomenon for C2H2 and C2H6 adsorption selectivity over C2H4 was observed. This trend also occurred in the 273 K C2 sorption isotherms. The C2H2 and C2H6 uptakes for NPU-1 exceed the values of 4.55/3.79 mmol g–1 for TJT-100 and 3.50/4.47 mmol g–1 for Azole-Th-1.

Adsorption selectivity is an important metric when evaluating separation performance. Ideal Adsorbed Solution Theory51 (IAST) was used to calculate the adsorption selectivity of C2H2/C2H4 and C2H6/C2H4 for equimolar gas mixtures at 298 K and 100 kPa, after fitting the single-component 298 K adsorption isotherms to the Langmuir–Freundlich equation (Supplementary Figures 16–18). The adsorption selectivity values for C2H6/C2H4 and C2H2/C2H4 were found to be 1.32 and 1.4 for NPU-1, 1.52 and 1.25 for NPU-2, and 3.21 and 1.32 for NPU-3 (Figure 2g), making the NPU-1/2/3 platform only the third reported example of C2H2 and C2H6 adsorption selectivity vs C2H4. The C2H6/C2H4 IAST selectivity values for NPU-1/2/3 are comparable to those of the other C2H6-selective sorbents (1.95 for MUF-15,52 1.8 for IRMOF-8,53 1.76 for NUM-7a,54 and 1.6 for JNU-2(55)).

To evaluate the interaction strengths of C2H2, C2H4, and C2H6 with NPU-1/2/3, the adsorption enthalpies (Qst) were calculated using the Clausius–Clapeyron equation by fitting the C2H2, C2H4, and C2H6 adsorption isotherms at 273 and 298 K to the virial equation (detailed fitting curves are given in Supplementary Figures 22–24). As expected, NPU-1/2/3 interact somewhat more strongly with C2H2 and C2H6 than with C2H4. Figure 2h presents C2H2 (27.88 kJ mol–1 for NPU-1, 20.98 kJ mol–1 for NPU-2, and 19.93 kJ mol–1 for NPU-3) and C2H6 (29.10 kJ mol–1 for NPU-1, 19.64 kJ mol–1 for NPU-2, and 18.71 kJ mol–1 for NPU-3) adsorption enthalpies relative to C2H4 (23.95 kJ mol–1 for NPU-1, 18.18 kJ mol–1 for NPU-2, and 17.79 kJ mol–1 for NPU-3) at low loadings. Considering the differences between the low C2 loading enthalpies, particularly those for C2H2 and C2H6, the decreasing Qst trend holds across the full C2 loading range: Qst(C2H2) ≈ Qst(C2H6) > Qst(C2H4). Increased adsorption enthalpy for C2 hydrocarbons with decreasing pore size can be attributed to stronger binding in tighter pores.11,56 We note that a relatively low adsorption enthalpy value means a relatively low energy footprint for sorbent regeneration.

Molecular simulations were performed to gain insight into the nature of the binding sites for C2H2, C2H4, and C2H6 in NPU-1 (see Supporting Information for full details). The modeling studies revealed that C2H2 localizes in a triangular pocket formed by two BDC linkers and one Tripp linker (Figure 3a). C2H2 molecules interact with electronegative carboxylate O atoms of the BDC linkers through their CH moieties. C2H2 molecules also interact with the aromatic rings of BDC and Tripp linkers. C2H4 was found to adsorb at the same location as C2H2, although its interaction distances are longer (Figure 3b), an indication that C2H4 is likely to exhibit weaker interactions with NPU-1. The calculated averaged classical potential energies for both adsorbates about this position (see Supporting Information for details) also support weaker interactions with C2H4. In essence, the D2h symmetry of C2H4 offers a less favorable fit compared to the D∞h symmetry of C2H2.

Figure 3.

Figure 3

Open in a new tab

Molecular modeling determined primary adsorption sites of (a) C2H2, (b) C2H4, and (c) C2H6 in NPU-1. Adsorbed C2 molecules are presented in space-filling mode (C(MOM), gray; C(C2 gas), orange; H, white; O, red; N, blue; Mn, purple).

In contrast to C2H2 and C2H4, C2H6 is too bulky to be adsorbed in the triangular channels, and the modeling studies suggested that the most favorable binding site for C2H6 is between two adjacent Tripp linkers (Figure 3c). Its larger molecular dimensions and the presence of multiple H atoms allow C2H6 to engage in multiple weak interactions with surrounding Tripp linkers. C2H6 can also interact with the phenyl ring of a nearby BDC linker. This binding site is quite favorable, as the potential energy for C2H6 at this site is comparable to that for C2H2 at its energy minimum position on the basis of simulated annealing calculations (see Supplementary Table 3). Overall, molecular simulations support the following trend in sorbent–sorbate interactions for NPU-1: C2H2 ≈ C2H6 > C2H4. This trend is consistent with the experimental findings.

To evaluate separation performance, dynamic column breakthrough experiments were performed for NPU-1 and NPU-2. Two separate columns with tightly packed powder samples of 2.9 g of NPU-1 and 2.5 g of NPU-2 were prepared by pre-activating at 353 K under He flow (flow rate of 20 cm3 min–1). In a typical breakthrough experiment at 298 K, a 1:1:1 mixture of C2H2/C2H4/C2H6 at a total gas pressure of 100 kPa was passed through the packed adsorbent column, and the outlet gas signal was detected by gas chromatography. As shown in Figure 4a, NPU-1 effectively captured C2H2 and C2H6 from the 1:1:1 gas mixture and afforded polymer-grade C2H4 in the effluent stream. Ethylene breakthrough occurred first at ca. 93 min, followed by C2H2 and C2H6 at ca. 100 min. Before the breakthrough of C2H2 and C2H6 from the column outlet, C2H4 with polymer-grade purity (>99.9%) was harvested, establishing the ability of NPU-1 to produce polymer-grade ethylene from 1:1:1 C2H2/C2H4/C2H6 in a single separation step. Furthermore, dynamic breakthrough experiments with less NPU-1 (1.3 g) exhibited similar separation performance but with slightly reduced working capacity (Supplementary Figure 31). For the NPU-2 column, the breakthrough curve follows the same time sequence (C2H4 first, C2H2 second, and C2H6 last) as NPU-1, but ethylene in high purity was not afforded because of the very close breakthrough times of C2H2 and C2H4. This result was presumably a consequence of the lower adsorption enthalpy of all three gases for NPU-2 vs NPU-1 and the minimal differences between C2H2 and C2H4 isotherms in NPU-2 at lower pressures. NPU-3, with even lower adsorption capacity and enthalpy, was not subjected to dynamic breakthrough experiments. To confirm the ease of regeneration of NPU-1, we conducted temperature-programmed desorption experiments after saturation of the separation column. As seen in Figure 4c, the NPU-1 column can be fully activated after heating at 313 K for 40 min under He flow (10 cm3 min–1). Upon increasing the activation temperature to 333 K, the regeneration time was reduced to 25 min. To test the recycling ability of NPU-1, 10 cycles of ternary gas mixture breakthrough and single-gas ethane adsorption experiments were conducted. No performance loss was detected. In addition, the PXRD pattern of NPU-1 collected after exposure to ambient air over a month verified its moisture stability.

Figure 4.

Figure 4

Open in a new tab

Dynamic breakthrough data and stability test. Experimental breakthrough curves at 298 K for C2H2/C2H4/C2H6 separation (1:1:1 mixture; total gas pressure of 100 kPa; total gas flow of 2.1 cm3 min–1) based on (a) NPU-1 column with 2.9 g sample and (b) NPU-2 column with 2.5 g sample. (c) Temperature-programmed desorption curves for NPU-1-packed column activated at 313 and 333 K under He flow of 20 cm3 min–1. (d) Dynamic breakthrough data of NPU-1 in the 1st, 5th, and 10th cycles for ternary gas separation (C, outlet gas concentration; C0, inlet gas concentration). (e) PXRD patterns of NPU-1 under different conditions. (f) Ten-cycle comparison of C2H6 adsorption capacity at 298 K and 100 kPa for NPU-1 (n0, C2H6 uptake for first cycle; n, C2H6 uptake for the specific cycle).

Conclusion

In summary, we report a new hexanuclear metal cluster, [Mn6(μ3-O)2(CH3COO)3]6+, that can serve as a node in three porous coordination networks (NPU-1/2/3) with the same pacs topology and high connectivity. Pore size and pore chemistry in the dual cages were controlled by linker ligand substitution, affording a pore environment suitable for effective separation of C2H2 and C2H6 from C2H4. NPU-1 thereby enabled production of polymer-grade ethylene from a 1:1:1 C2H2/C2H4/C2H6 gas mixture at ambient conditions in one step. Sorbent–sorbate interactions, as delineated by molecular simulations, revealed that the dual cage nature of NPU-1 is the reason for the observed performance.

Acknowledgments

K.-J.C. appreciates the financial support from the National Natural Science Foundation of China (22071195 and 21805227), Fundamental Research Funds for the Central Universities (3102017jc01001) and The Youth Innovation Team of Shaanxi Universities. M.J.Z. acknowledges the generous support of Science Foundation Ireland (awards 13/RP/B2549 and 16/IA/4624). B.Z. appreciates the Project of Shandong Province Higher Educational Science and Technology Program (J16LC06). T.W. thanks the National Natural Science Foundation of China (No. 21905229) and the Natural Science Basic Research Plan in Shanxi Province of China (No. 2019JQ627) for support. T.P. and K.A.F. acknowledge Prof. Brian Space for helpful discussions and computational resources made available by his XSEDE Grant (No. TG-DMR090028) and the services provided by Research Computing at the University of South Florida. We are grateful for Dr. Hui Wang and Jie Li for their contributions to molecular simulations and ligand synthesis.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c11247.

  • Experimental details and characterization discussion, XRD patterns, sorption data, thermogravimetric analysis data, breakthrough experiment data of NPU-1/2/3, molecular simulations detail of NPU-1, and supplementary figures and tables (PDF)

Accession Codes

CCDC 2032374–2032376 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

Author Contributions

† B.Z. and J.-W.C. contributed equally in this work.

The authors declare no competing financial interest.

This paper was initially published January 13, 2021, with an incorrect copyright line. The copyright was corrected and the paper reposted June 8, 2021.

Supplementary Material

ja0c11247_si_001.pdf (10MB, pdf)

References

  1. Ethylene (ET): 2019 World Market Outlook and Forecast up to 2023, from https://www.researchandmarkets.com (retrieved Jan 2019).
  2. Sholl D. S.; Lively R. P. Seven chemical separations to change the world. Nature 2016, 532, 435–437. 10.1038/532435a. [DOI] [PubMed] [Google Scholar]
  3. Ren T.; Patel M.; Blok K. Olefins from conventional and heavy feedstocks: Energy use in steam cracking and alternative processes. Energy 2006, 31, 425–451. 10.1016/j.energy.2005.04.001. [DOI] [Google Scholar]
  4. Li J.-R.; Kuppler R. J.; Zhou H.-C. Selective gas adsorption and separation in metal-organic frameworks. Chem. Soc. Rev. 2009, 38, 1477–1504. 10.1039/b802426j. [DOI] [PubMed] [Google Scholar]
  5. Perry IV J. J.; Perman J. A.; Zaworotko M. J. Design and synthesis of metal-organic frameworks using metal-organic polyhedra as supermolecular building blocks. Chem. Soc. Rev. 2009, 38, 1400–1417. 10.1039/b807086p. [DOI] [PubMed] [Google Scholar]
  6. MacGillivray L.-R.Preface. In Metal-Organic Frameworks: Design and Application; MacGillivray L.-R., Ed.; Wiley, Hoboken, NJ, 2010. [Google Scholar]
  7. Furukawa H.; Cordova K.-E.; O’Keeffe M.; Yaghi O.-M. The chemistry and applications of metal-organic frameworks. Science 2013, 341, 974. 10.1126/science.1230444. [DOI] [PubMed] [Google Scholar]
  8. Kitagawa S.; Kitaura R.; Noro S. Functional porous coordination polymers. Angew. Chem., Int. Ed. 2004, 43, 2334–2375. 10.1002/anie.200300610. [DOI] [PubMed] [Google Scholar]
  9. Moulton B.; Zaworotko M.-J. From molecules to crystal engineering: Supramolecular isomerism and polymorphism in network solids. Chem. Rev. 2001, 101, 1629–1658. 10.1021/cr9900432. [DOI] [PubMed] [Google Scholar]
  10. Eddaoudi M.; Kim J.; Rosi N.; Vodak D.; Wachter J.; O’Keeffe M.; Yaghi O.-M. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 2002, 295, 469–472. 10.1126/science.1067208. [DOI] [PubMed] [Google Scholar]
  11. Cui X.-L.; Chen K.-J.; Xing H.-B.; Yang Q.-W.; Krishna R.; Bao Z.-B.; Wu H.; Zhou W.; Dong X.-L.; Han Y.; Li B.; Ren Q.-L.; Zaworotko M.-J.; Chen B.-L. Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene. Science 2016, 353, 141–144. 10.1126/science.aaf2458. [DOI] [PubMed] [Google Scholar]
  12. Mukherjee S.; Sensharma D.; Chen K.-J.; Zaworotko M.-J. Crystal engineering of porous coordination networks to enable separation of C2 hydrocarbons. Chem. Commun. 2020, 56, 10419–10441. 10.1039/D0CC04645K. [DOI] [PubMed] [Google Scholar]
  13. Liao P.-Q.; Zhang W.-X.; Zhang J.-P.; Chen X.-M. Efficient purification of ethene by an ethane-trapping metal-organic framework. Nat. Commun. 2015, 6, 8697. 10.1038/ncomms9697. [DOI] [PMC free article] [PubMed] [Google Scholar]
  14. Li L.-B.; Lin R.-B.; Krishna R.; Li H.; Xiang S.-C.; Wu H.; Li J.-P.; Zhou W.; Chen B.-L. Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites. Science 2018, 362, 443–446. 10.1126/science.aat0586. [DOI] [PubMed] [Google Scholar]
  15. Yang H.-J.; Wang Y.-X.; Krishna R.; Jia X.-X.; Wang Y.; Hong A.-N.; Dang C.; Castillo H.-E.; Bu X.-H.; Feng P.-Y. Pore-space-partition-enabled exceptional ethane uptake and ethane-selective ethane-ethylene separation. J. Am. Chem. Soc. 2020, 142, 2222–2227. 10.1021/jacs.9b12924. [DOI] [PubMed] [Google Scholar]
  16. Yang S.-H.; Ramirez-Cuesta A.-J; Newby R.; Garcia-Sakai V.; Manuel P.; Callear S.-K.; Campbell S.-I; Tang C.-C.; Schröder M. Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework. Nat. Chem. 2015, 7, 121–129. 10.1038/nchem.2114. [DOI] [PubMed] [Google Scholar]
  17. Ding Q.; Zhang Z.-Q.; Yu C.; Zhang P.-X.; Wang J.; Cui X.-L.; He C.-H.; Deng S.-G.; Xing H.-B. Exploiting equilibrium-kinetic synergetic effect for separation of ethylene and ethane in a microporous metal-organic framework. Sci. Adv. 2020, 6, eaaz4322 10.1126/sciadv.aaz4322. [DOI] [PMC free article] [PubMed] [Google Scholar]
  18. Bloch E.-D.; Queen W.-L.; Krishna R.; Zadrozny J.-M.; Brown C.-M.; Long J.-R. Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites. Science 2012, 335, 1606–1610. 10.1126/science.1217544. [DOI] [PubMed] [Google Scholar]
  19. Li B.; Cui X.-L.; O’Nolan D.; Wen H.-M.; Jiang M.-D.; Krishna R.; Wu H.; Lin R.-B.; Chen Y.-S.; Yuan D.-Q.; Xing H.-B.; Zhou W.; Ren Q.-L.; Qian G.-D.; Zaworotko M.-J.; Chen B.-L. An ideal molecular sieve for acetylene removal from ethylene with record selectivity and productivity. Adv. Mater. 2017, 29, 1704210. 10.1002/adma.201704210. [DOI] [PubMed] [Google Scholar]
  20. Pei J.; Shao K.; Wang J.-X.; Wen H.-M.; Yang Y.; Cui Y.; Krishna R.; Li B.; Qian G. A chemically stable hofmann-type metal-organic framework with sandwich-like binding sites for benchmark acetylene capture. Adv. Mater. 2020, 32, 1908275. 10.1002/adma.201908275. [DOI] [PubMed] [Google Scholar]
  21. Peng Y.-L.; Pham T.; Li P.-F.; Wang T.; Chen Y.; Chen K.-J.; Forrest K.-A.; Space B.; Cheng P.; Zaworotko M.-J.; Zhang Z.-J. Robust ultramicroporous metal–organic frameworks with benchmark affinity for acetylene. Angew. Chem., Int. Ed. 2018, 57, 10971–10975. 10.1002/anie.201806732. [DOI] [PubMed] [Google Scholar]
  22. Xiang S.-C.; Zhang Z.-J.; Zhao C.-G.; Hong K.-L.; Zhao X.-B.; Ding D.-R.; Xie M.-H.; Wu C.-D.; Das M.-C.; Gill R.; Thomas K.-M.; Chen B.-L. Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene. Nat. Commun. 2011, 2, 204. 10.1038/ncomms1206. [DOI] [PubMed] [Google Scholar]
  23. Qazvini O.-T.; Babarao R.; Telfer S.-G. Multipurpose metal–organic framework for the adsorption of acetylene: ethylene purification and carbon dioxide removal. Chem. Mater. 2019, 31, 4919–4926. 10.1021/acs.chemmater.9b01691. [DOI] [Google Scholar]
  24. Sun F.-Z.; Yang S.-Q.; Krishna R.; Zhang Y.-H.; Xia Y.-P.; Hu T.-L. Microporous metal–organic framework with a completely reversed adsorption relationship for C2 hydrocarbons at room temperature. ACS Appl. Mater. Interfaces 2020, 12, 6105–6111. 10.1021/acsami.9b22410. [DOI] [PubMed] [Google Scholar]
  25. Zhao X.; Wang Y.-X.; Li D.-S.; Bu X.-H.; Feng P.-Y. Metal–organic frameworks for separation. Adv. Mater. 2018, 30, 1705189. 10.1002/adma.201705189. [DOI] [PubMed] [Google Scholar]
  26. Lee J.; Chuah C.-Y.; Kim J.; Kim Y.; Ko N.; Seo Y.; Kim K.; Bae T.-H.; Lee E. Separation of acetylene from carbon dioxide and ethylene by a water-stable microporous metal–organic framework with aligned imidazolium groups inside the channels. Angew. Chem., Int. Ed. 2018, 57, 7869–7873. 10.1002/anie.201804442. [DOI] [PubMed] [Google Scholar]
  27. Ke T.; Wang Q.-J; Shen J.; Zhou J.-Y; Bao Z.-B; Yang Q.-W.; Ren Q.-L. Molecular sieving of C2-C3 alkene from alkyne with tuned threshold pressure in robust layered metal–organic frameworks. Angew. Chem., Int. Ed. 2020, 59, 12725–12730. 10.1002/anie.202003421. [DOI] [PubMed] [Google Scholar]
  28. Zhang Y.-B.; Hu J.-B.; Krishna R.; Wang L.-Y.; Yang L.-F.; Cui X.-L.; Duttwyler S.; Xing H.-B. Rational design of microporous MOFs with anionic boron cluster functionality and cooperative dihydrogen binding sites for highly selective capture of acetylene. Angew. Chem., Int. Ed. 2020, 59, 17664–17669. 10.1002/anie.202007681. [DOI] [PubMed] [Google Scholar]
  29. Lysova A.-A.; Samsonenko D.-G.; Kovalenko K.-A.; Nizovtsev A.-S.; Dybtsev D.-N.; Fedin V.-P. A series of mesoporous metal-organic frameworks with tunable windows sizes and exceptionally high ethane over ethylene adsorption selectivity. Angew. Chem., Int. Ed. 2020, 59, 20561. 10.1002/anie.202008132. [DOI] [PubMed] [Google Scholar]
  30. Zhang Z.-Q.; Peh S.-B.; Wang Y.-X.; Kang C.-J.; Fan W.-D.; Zhao D. Efficient trapping of trace acetylene from ethylene in an ultramicroporous metal–organic framework: synergistic effect of high-density open metal and electronegative sites. Angew. Chem., Int. Ed. 2020, 59, 18927–18932. 10.1002/anie.202009446. [DOI] [PubMed] [Google Scholar]
  31. Wang J.-W.; Li L.-Y.; Guo L.-D.; Zhao Y.-C; Xie D.-Y.; Zhang Z.-G.; Yang Q.-W.; Yang Y.-W.; Bao Z.-B; Ren Q.-L. Adsorptive separation of acetylene from ethylene in isostructural gallate-based metal–organic frameworks. Chem. - Eur. J. 2019, 25, 15516–15524. 10.1002/chem.201903952. [DOI] [PubMed] [Google Scholar]
  32. Li J.; Jiang L.-Y.; Chen S.; Kirchon A.; Li B.; Li Y.–S.; Zhou H.-C. Metal–organic framework containing planar metal-binding sites: efficiently and cost-effectively enhancing the kinetic separation of C2H2/C2H4. J. Am. Chem. Soc. 2019, 141, 3807–3811. 10.1021/jacs.8b13463. [DOI] [PubMed] [Google Scholar]
  33. Hao H.-G.; Zhao Y.-F.; Chen D.-M.; Yu J.-M.; Tan K.; Ma S.-Q.; Chabal Y.; Zhang Z.-M.; Dou J.-M.; Xiao Z.-H.; Day G.; Zhou H.-C.; Lu T.-B. Simultaneous trapping of C2H2 and C2H6 from a ternary mixture of C2H2/C2H4/C2H6 in a robust metal-organic framework for the purification of C2H4. Angew. Chem., Int. Ed. 2018, 57, 16067–16071. 10.1002/anie.201809884. [DOI] [PubMed] [Google Scholar]
  34. Chen K.-J.; Madden D.-G.; Mukherjee S.; Pham T.; Forrest K.-A.; Kumar A.; Space B.; Kong J.; Zhang Q.-Y.; Zaworotko M.-J. Synergistic sorbent separation for one-step ethylene purification from a four-component mixture. Science 2019, 366, 241–246. 10.1126/science.aax8666. [DOI] [PubMed] [Google Scholar]
  35. Xu Z.-Z.; Xiong X.-H.; Xiong J.-B.; Krishna R.; Li L.-B.; Fan Y.-L.; Luo F.; Chen B.-L. A robust Th-azole framework for highly efficient purification of C2H4 from a C2H4/C2H2/C2H6 mixture. Nat. Commun. 2020, 11, 3163. 10.1038/s41467-020-16960-9. [DOI] [PMC free article] [PubMed] [Google Scholar]
  36. Figgis B.-N.; Robertson G.-B. Crystal-molecular structure and magnetic properties of Cr3(CH3COO)6OCl.5H2O. Nature 1965, 205, 694–695. 10.1038/205694a0. [DOI] [Google Scholar]
  37. Polunin R.-A.; Kolotilov S.-V.; Kiskin M.-A.; Cador O.; Mikhalyova E.-A.; Lytvynenko A.-S.; Golhen S.; Ouahab L.; Ovcharenko V.-I.; Eremenko I.-L.; Novotortsev V.-M.; Pavlishchuk V.-V. Topology control of porous coordination polymers by building block symmetry. Eur. J. Inorg. Chem. 2010, 2010, 5055–5057. 10.1002/ejic.201000929. [DOI] [Google Scholar]
  38. Férey G.; Mellot-Draznieks C.; Serre C.; Millange F.; Dutour J.; Surblé S.; Margiolaki I. A chromium terephthalate-based solid with unusually large pore volumes and surface area. Science 2005, 309, 2040–2042. 10.1126/science.1116275. [DOI] [PubMed] [Google Scholar]
  39. Zhang Y.-B.; Zhang W.-X.; Feng F.-Y.; Zhang J.-P.; Chen X.-M. A highly connected porous coordination polymer with unusual channel structure and sorption properties. Angew. Chem., Int. Ed. 2009, 48, 5287–5290. 10.1002/anie.200901964. [DOI] [PubMed] [Google Scholar]
  40. Wei Y.-S.; Chen K.-J.; Liao P.-Q.; Zhu B.-Y.; Lin R.-B.; Zhou H.-L.; Wang B.-Y.; Xue W.; Zhang J.-P.; Chen X.-M. Turning on the flexibility of isoreticular porous coordination frameworks for drastically tunable framework breathing and thermal expansion. Chem. Sci. 2013, 4, 1539–1546. 10.1039/c3sc22222e. [DOI] [Google Scholar]
  41. Zhao X.; Bu X.-H.; Zhai Q.-G.; Tran H.; Feng P.-Y. Pore space partition by symmetry-matching regulated ligand insertion and dramatic tuning on carbon dioxide uptake. J. Am. Chem. Soc. 2015, 137, 1396–1399. 10.1021/ja512137t. [DOI] [PubMed] [Google Scholar]
  42. Cairns A.-J.; Perman J.-A.; Wojtas L.; Kravtsov V.-C.; Alkordi M.-H.; Eddaoudi M.; Zaworotko M.-J. Supermolecular building blocks (SBBs) and crystal design: 12-connected open frameworks based on a molecular cubohemioctahedron. J. Am. Chem. Soc. 2008, 130, 1560–1561. 10.1021/ja078060t. [DOI] [PubMed] [Google Scholar]
  43. Robinson S. A. K.; Mempin M. V. L.; Cairns A. J.; Holman K.-T. A cubic, 12-connected, microporous metal-organometallic phosphate framework sustained by truncated tetrahedral nodes. J. Am. Chem. Soc. 2011, 133, 1634–1637. 10.1021/ja108894a. [DOI] [PubMed] [Google Scholar]
  44. Cavka J. H.; Jakobsen S.; Olsbye U.; Guillou N.; Lamberti C.; Bordiga S.; Lillerud K.-P. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. J. Am. Chem. Soc. 2008, 130, 13850–13851. 10.1021/ja8057953. [DOI] [PubMed] [Google Scholar]
  45. Zhao X.; Bu X.-H.; Wu T.; Zheng S.-T.; Wang L.; Feng P.-Y. Selective anion exchange with nanogated isoreticular positive metal-organic frameworks. Nat. Commun. 2013, 4, 2344. 10.1038/ncomms3344. [DOI] [PubMed] [Google Scholar]
  46. Zhai Q.-G.; Bu X.-H.; Zhao X.; Li D.-S.; Feng P.-Y. Pore Space Partition in Metal–Organic Frameworks. Acc. Chem. Res. 2017, 50, 407–417. 10.1021/acs.accounts.6b00526. [DOI] [PubMed] [Google Scholar]
  47. Perry J. J. IV.; Kravtsov V.-C.; McManus G.-J.; Zaworotko M.-J. Bottom up synthesis that does not start at the bottom: quadruple covalent cross-linking of nanoscale faceted polyhedra. J. Am. Chem. Soc. 2007, 129, 10076–10077. 10.1021/ja0734952. [DOI] [PubMed] [Google Scholar]
  48. Nouar F.; Eubank J.-F.; Bousquet T.; Wojtas L.; Zaworotko M.-J.; Eddaoudi M. Supermolecular building blocks (SBBs) for the design and synthesis of highly porous metal-organic frameworks. J. Am. Chem. Soc. 2008, 130, 1833–1835. 10.1021/ja710123s. [DOI] [PubMed] [Google Scholar]
  49. Spek A. L. Structure validation in chemical crystallography. Acta Crystallogr., Sect. D: Biol. Crystallogr. 2009, 65, 148–155. 10.1107/S090744490804362X. [DOI] [PMC free article] [PubMed] [Google Scholar]
  50. Nugent P.; Belmabkhout Y.; Burd S.-D.; Cairns A.-J.; Luebke R.; Forrest K.; Pham T.; Ma S.-Q.; Space B.; Wojtas L.; Eddaoudi M.; Zaworotko M.-J. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation. Nature 2013, 495, 80–84. 10.1038/nature11893. [DOI] [PubMed] [Google Scholar]
  51. Myers A.-L.; Prausnitz J.-M. Thermodynamics of Mixed-gas Adsorption. AIChE J. 1965, 11, 121. 10.1002/aic.690110125. [DOI] [Google Scholar]
  52. Qazvini O.-T.; Babarao R.; Shi Z.-L.; Zhang Y.-B.; Telfer S.-G. A Robust Ethane-Trapping Metal–Organic Framework with a High Capacity for Ethylene Purification. J. Am. Chem. Soc. 2019, 141, 5014–5020. 10.1021/jacs.9b00913. [DOI] [PubMed] [Google Scholar]
  53. Pires J.; Pinto M.-L.; Saini V.-K. Ethane Selective IRMOF-8 and Its Significance in Ethane-Ethylene Separation by Adsorption. ACS Appl. Mater. Interfaces 2014, 6, 12093–12099. 10.1021/am502686g. [DOI] [PubMed] [Google Scholar]
  54. Sun F.-Z.; Yang S.-Q.; Krishna R.; Zhang Y.-H.; Xia Y.-P.; Hu T.-L. Microporous Metal-Organic Framework with a Completely Reversed Adsorption Relationship for C-2 Hydrocarbons at Room Temperature. ACS Appl. Mater. Interfaces 2020, 12, 6105–6111. 10.1021/acsami.9b22410. [DOI] [PubMed] [Google Scholar]
  55. Zeng H.; Xie X.-J.; Xie M.; Huang Y.-L.; Luo D.; Wang T.; Zhao Y.-F.; Lu W.-G.; Li D. Cage-Interconnected Metal-Organic Framework with Tailored Apertures for Efficient C2H6/C2H4 Separation under Humid Conditions. J. Am. Chem. Soc. 2019, 141, 20390–20396. 10.1021/jacs.9b10923. [DOI] [PubMed] [Google Scholar]
  56. Jiang X.; Zhang T.; Cao J.-W.; Zhao C.-K.; Yang R.; Zhang Q.-Y.; Chen K.-J. Effect of Pore Size on the Separation of Ethylene from Ethane in Three Isostructural Metal Azolate Frameworks. Inorg. Chem. 2020, 59, 13019–13023. 10.1021/acs.inorgchem.0c02229. [DOI] [PubMed] [Google Scholar]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

ja0c11247_si_001.pdf (10MB, pdf)

Articles from Journal of the American Chemical Society are provided here courtesy of American Chemical Society

RESOURCES