Chemcomm Acceptedchemical Communications Manuscript

View Article Online View Journal ChemComm AcceptedChemical Communications Manuscript This article can be cited before page numbers have been issued, to do this please use: M. zaworotko, D. O'Nolan, D. Madden, A. Kumar, K. J. Chen, T. Pham, K. Forrest, E. Patyk-Kazmierczak, Q. Y. Yang, C. Murray, C. Tang and B. Space, Chem. Commun., 2018, DOI: 10.1039/C8CC01627E. Volume 52 Number 1 4 January 2016 Pages 1–216 This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been ChemComm accepted for publication. Chemical Communications Accepted Manuscripts are published online shortly after www.rsc.org/chemcomm acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available. You can find more information about Accepted Manuscripts in the author guidelines. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s ISSN 1359-7345 standard Terms & Conditions and the ethical guidelines, outlined in our author and reviewer resource centre, still apply. In no COMMUNICATION Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyen et al. Reactivity diff erences of Sc3N@C2n (2n = 68 and 80). Synthesis of the ﬁ rst methanofullerene derivatives of Sc N@D -C 3 5h 80 event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. rsc.li/chemcomm Page 1 of 5 Please do not adjust margins ChemComm View Article Online DOI: 10.1039/C8CC01627E Journal Name COMMUNICATION . Impact of Partial Interpenetration in a Hybrid Ultramicroporous Material on C2H2/C2H4 Separation Performance Received 00th January 20xx, [a] [a] [a] [a] [b] Accepted 00th January 20xx Daniel O’Nolan, David G. Madden, Amrit Kumar, Kai‐Jie Chen, Tony Pham, Katherine A. Forrest, [b] Ewa Patyk‐Kazmierczak, [a] Qing‐Yuan Yang, [a] Claire A. Murray, [c] Chiu C. Tang, [c] Brian DOI: 10.1039/x0xx00000x Space, [b] and Michael J. Zaworotko[a]* www.rsc.org/ Phases of a 2‐fold pcu Hybrid Ultramicroporous Material (HUM), pcu, structures in which fluorine atoms create a binding site SIFSIX‐14‐Cu‐i, exhibiting 99%, 93%, 89%, and 70% partial for CO2 molecules. The resulting induced‐dipole interactions interpenetration have been obtained. 1:99 C2H2/C2H4 gas enable benchmark performance for CO2 capture from CO2/CH4 separation studies reveal that as the proportion of and CO2/N2 gas mixtures, separations that are important to interpenetrated component decreases, so does the separation natural gas processing and greenhouse gas sequestration, performance. respectively. Similarly, the 2‐fold interpenetrated HUMs SIFSIX‐2‐Cu‐i15a and SIFSIX‐14‐Cu‐i (also termed UTSA‐ The design of porous coordination networks through crystal 200),10a,15b which also exhibit pcu topology, afford benchmark 1 2 engineering and reticular chemistry principles has yielded a performance for separation of C2H2 from C2H4 gas streams, rich tapestry of porous metal‐organic materials, MOMs3 (e.g. separation relevant to polyethylene production. The porous coordination polymers,4 PCPs, and metal‐organic separation performances in these cases are the result of offset frameworks,5 MOFs) and hybrid ultramicroporous materials, inorganic pillars that create preferential H‐bonding sites for 6 HUMs. These classes of porous materials have provided C2H2 that are unfavorable for C2H4 adsorption. understanding about phenomena such as topology,7 Whereas interpenetration is key to creating the tight binding interpenetration,8 post‐synthetic modification,9 and guest‐ sites that enable the benchmark selectivity of SIFSIX‐2‐Cu‐i induced phase transformations in porous coordination and SIFSIX‐14‐Cu‐i, it also reduces surface area and working networks.10 In effect, crystal engineering has evolved from its capacity. Given that gas separations are dependent upon both original focus upon design of new crystalline materials into the selectivity for one molecule over another and the working design of a new generation of task‐specific materials for use in capacity of a material, physisorbents suited for industrial use catalysis,11 gas storage,12 and gas separation.13 would need to optimally balance for selectivity and working In the context of gas separations, major strides have recently capacity. Recent reports that partial interpenetration can been made with respect to the physisorptive purification of occur in MOMs20 suggest that such an optimal balance several industrially important feedstocks as new selectivity between selectivity and working capacity might occur in a 14 benchmarks have been set for gas mixtures such as CO2/N2, 15 16 17 C2H2/C2H4, C2H2/CO2, Xe/Kr, and direct air capture of 18 19 CO2 and water. With respect to HUMs, the combination of ultramicropores (pore diameter < 0.7 nm) lined with inorganic walls has enabled a relatively straightforward approach to control over pore size and chemistry that can afford molecular ChemComm Accepted Manuscript traps for targeted gas molecules. Indeed, TIFSIX‐3‐Ni,18a NbOFFIVE‐1‐Ni,18b and SIFSIX‐3‐Zn14a exhibit primitive cubic, a. Bernal Institute, Department of Chemical Sciences, University of Limerick, Limerick, V94 T9PX, Ireland b. Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, CHE205, Tampa, Florida 33620, United States c. Diamond Light Source Ltd, Harwell Science and Innovation Campus, Didcot, Oxfordshire, UK † Footnotes relating to the title and/or authors should appear here. Fig. 1. 77 K N2 adsorption isotherms for phases 1, 2, 3 and 4. As the proportion of the Electronic Supplementary Information (ESI) available: [details of any microporous non‐interpenetrated component increases vs. the ultramicroporous 2‐ supplementary information available should be included here]. See fold interpenetrated component, so does the N2 uptake DOI: 10.1039/x0xx00000x This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1‐3 | 1 Please do not adjust margins Please do not adjust margins ChemComm Page 2 of 5 View Article Online DOI: 10.1039/C8CC01627E COMMUNICATION Journal Name porous material that is a solid solution21 of interpenetrated at 77 K of 643.4 cm3/g for SIFSIX‐14‐Cu (calculated) and no and non‐interpenetrated components. This is because, in uptake for SIFSIX‐14‐Cu‐i (experimental).15b The proportions of principle, such a phase could offer the best of both worlds with interpenetrated and non‐interpenetrated phases within each respect to high selectivity (interpenetration leading to sample were estimated from quantitative phase analysis using ultramicropores) and working capacity (non‐interpenetration synchrotron PXRD data. The quantitative phase analysis and 20b leading to micropores and more uptake). Herein, we test N2 adsorption data were collectively used to estimate the this hypothesis via a study of partial interpenetration and the phase fraction for 1‐4 (See Supporting Information). 1 is separation properties of the recently reported 2‐fold estimated to be the purest phase of SIFSIX‐14‐Cu‐i (ca. 99% 2‐ interpenetrated HUM, SIFSIX‐14‐Cu‐i,10a,15b the current fold interpenetrated content), whereas 2 – 4 are estimated to benchmark for trace removal of C2H2 from C2H4. consist of 93%, 89%, and 70% 2‐fold interpenetration, . Partial interpenetration in SIFSIX‐14‐Cu‐i was achieved by respectively (See Figure 2 and Supporting Information). variation of synthetic conditions and methods. We have In order to confirm that the partially interpenetrated phases previously found that temperature and concentration can be are indeed solid solutions as opposed to being physical used to assert control over interpenetration.22 Herein, four mixtures of interpenetrated and non‐interpenetrated phases, phases were synthesized solvothermally in methanol at 120 °C; thermogravimetric analysis (TGA) and differential scanning reaction duration and reaction vessel type were varied. Phase calorimetry (DSC) experiments were conducted (See 1 was isolated after reaction in a Parr® Teflon Bomb for 1 hour. Supporting Information). TGA experiments indicated that each Phases 2, 3 and 4 were prepared using variations of the sample had a similar onset melting point (Tm) within the range originally described method;10a reactions were conducted in of ca. 205 °C – 220 °C. DSC experiments all showed similar Schott® glass bottles and heated for 1 hour, 1 day, and 1 week, endotherms between ca. 160 °C and ca. 270 °C, wherein the respectively. The resulting solid products were repeatedly melt and decomposition of each sample resulted in the same exchanged with fresh dry methanol until the solvent was clear. peak shapes at approximately the same temperatures. Phases 1‐4 were at no point exposed to air, being submerged Following previous work on the separation of interpenetrated in methanol before being either dried in‐situ or air‐sealed and non‐interpenetrated structures,23 samples were added to during characterization experiments. an immiscible density gradient of n‐hexane (ρcalc = 0.655 3 3 Laboratory powder X‐ray diffraction (PXRD) experiments g/cm ) and DMSO (ρcalc = 1.1 g/cm ). The different densities of 3 indicated that longer reaction times afforded additional SIFSIX‐14‐Cu

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