Ethane/Ethylene Separations in Flexible Diamondoid Coordination Networks via an Ethane-Induced Gate-Opening Mechanism.

Separating ethane (C2H6) from ethylene (C2H4) is an essential and energy-intensive process in the chemical industry. Here, we report two flexible diamondoid coordination networks, X-dia-1-Ni and X-dia-1-Ni0.89Co0.11, that exhibit gate-opening between narrow-pore (NP) and large-pore (LP) phases for C2H6, but not for C2H4. X-dia-1-Ni0.89Co0.11 thereby exhibited a type F-IV isotherm at 273 K with no C2H6 uptake and a high uptake (111 cm3 g-1, 1 atm) for the NP and LP phases, respectively. Conversely, the LP phase exhibited a low uptake of C2H4 (12.2 cm3 g-1). This C2H6/C2H4 uptake ratio of 9.1 for X-dia-1-Ni0.89Co0.11 far surpassed those of previously reported physisorbents, many of which are C2H4-selective. In situ variable-pressure X-ray diffraction and modeling studies provided insight into the abrupt C2H6-induced structural NP to LP transformation. The promise of pure gas isotherms and, more generally, flexible coordination networks for gas separations was validated by dynamic breakthrough studies, which afforded high-purity (99.9%) C2H4 in one step.

Crystal Engineering of Two Light and Pressure Responsive Physisorbents.

An emerging strategy in the design of efficient gas storage technologies is the development of stimuli-responsive physisorbents which undergo transformations in response to a particular stimulus, such as pressure, heat or light. Herein, we report two isostructural light modulated adsorbents (LMAs) containing bis-3-thienylcyclopentene (BTCP), LMA-1 [Cd(BTCP)(DPT)2 ] (DPT=2,5-diphenylbenzene-1,4-dicarboxylate) and LMA-2 [Cd(BTCP)(FDPT)2 ] (FDPT=5-fluoro-2,diphenylbenzene-1,4-dicarboxylate). Both LMAs undergo pressure induced switching transformations from non-porous to porous via adsorption of N2 , CO2 and C2 H2 . LMA-1 exhibited multi-step adsorption while LMA-2 showed a single-step adsorption isotherm. The light responsive nature of the BTPC ligand in both frameworks was exploited with irradiation of LMA-1 resulting in a 55 % maximum reduction of CO2 uptake at 298 K. This study reports the first example of a switching sorbent (closed to open) that can be further modulated by light.

Highly Robust Microporous Metal-Organic Frameworks for Efficient Ethylene Purification under Dry and Humid Conditions.

Two C2 H6 -selective metal-organic framework (MOF) adsorbents with ultrahigh stability, high surface areas, and suitable pore size have been designed and synthesized for one-step separation of ethane/ethylene (C2 H6 /C2 H4 ) under humid conditions to produce polymer-grade pure C2 H4 . Experimental results reveal that these two MOFs not only adsorb a high amount of C2 H6 but also display good C2 H6 /C2 H4 selectivity verified by fixed bed column breakthrough experiments. Most importantly, the good water stability and hydrophobic pore environments make these two MOFs capable of efficiently separating C2 H6 /C2 H4 under humid conditions, exhibiting the benchmark performance among all reported adsorbents for separation of C2 H6 /C2 H4 under humid conditions. Moreover, the affinity sites and their static adsorption energies were successfully revealed by single crystal data and computation studies. Adsorbents described in this work can be used to address major chemical industrial challenges.

Metal-Organic Framework Based Hydrogen-Bonding Nanotrap for Efficient Acetylene Storage and Separation.

The removal of carbon dioxide (CO2) from acetylene (C2H2) is a critical industrial process for manufacturing high-purity C2H2. However, it remains challenging to address the tradeoff between adsorption capacity and selectivity, on account of their similar physical properties and molecular sizes. To overcome this difficulty, here we report a novel strategy involving the regulation of a hydrogen-bonding nanotrap on the pore surface to promote the separation of C2H2/CO2 mixtures in three isostructural metal-organic frameworks (MOFs, named MIL-160, CAU-10H, and CAU-23, respectively). Among them, MIL-160, which has abundant hydrogen-bonding acceptors as nanotraps, can selectively capture acetylene molecules and demonstrates an ultrahigh C2H2 storage capacity (191 cm3 g-1, or 213 cm3 cm-3) but much less CO2 uptake (90 cm3 g-1) under ambient conditions. The C2H2 adsorption amount of MIL-160 is remarkably higher than those for the other two isostructural MOFs (86 and 119 cm3 g-1 for CAU-10H and CAU-23, respectively) under the same conditions. More importantly, both simulation and experimental breakthrough results show that MIL-160 sets a new benchmark for equimolar C2H2/CO2 separation in terms of the separation potential (Δqbreak = 5.02 mol/kg) and C2H2 productivity (6.8 mol/kg). In addition, in situ FT-IR experiments and computational modeling further reveal that the unique host-guest multiple hydrogen-bonding interaction between the nanotrap and C2H2 is the key factor for achieving the extraordinary acetylene storage capacity and superior C2H2/CO2 selectivity. This work provides a novel and powerful approach to address the tradeoff of this extremely challenging gas separation.

Significantly Enhanced Carbon Dioxide Selective Adsorption via Gradual Acylamide Truncation in MOFs: Experimental and Theoretical Research.

A gradual amide truncation strategy was presented to tune the pore chemistry and CO2 capture performance of a series of tetracarboxylate-based Cu-MOFs. These MOFs exhibited a high density of Lewis basic sites (LBSs) and open metal sites and were prepared with the goal to enhance CO2 selective adsorption capacity. [Cu2(L1)(H2O)2]n (NJU-Bai42: NJU-Bai for Nanjing University Bai's group), [Cu2(L2) (H2O)2]n (NJU-Bai17), and [Cu2(L3)(H2O)2]n (NTUniv-60: NTUniv for Nantong University) were synthesized, and we observed that the CO2 adsorption capacities and MOF structures were impacted by subtle changes in ligands. Interestingly, although the NTUniv-60 was decorated with the least LBSs in these three MOFs, its CO2 adsorption capacity reached 270 (53.0 wt %) and 164 (32.2 wt %) cm3 g-1 at 273 and 296 K under 1 bar, respectively, which is the highest data reported for MOFs under similar conditions. From the grand canonical Monte Carlo (GCMC) simulation, the cooperative interactions between the CO2 molecules within the shuttle-shaped cages of NTUniv-60 could potentially explain why the CO2 uptake is high in this material.

Self-Adjusting Metal-Organic Framework for Efficient Capture of Trace Xenon and Krypton.

The capture of the xenon and krypton from nuclear reprocessing off-gas is essential to the treatment of radioactive waste. Although various porous materials have been employed to capture Xe and Kr, the development of high-performance adsorbents capable of trapping Xe/Kr at very low partial pressure as in the nuclear reprocessing off-gas conditions remains challenging. Herein, we report a self-adjusting metal-organic framework based on multiple weak binding interactions to capture trace Xe and Kr from the nuclear reprocessing off-gas. The self-adjusting behavior of ATC-Cu and its mechanism have been visualized by the in-situ single-crystal X-ray diffraction studies and theoretical calculations. The self-adjusting behavior endows ATC-Cu unprecedented uptake capacities of 2.65 and 0.52 mmol g-1 for Xe and Kr respectively at 0.1 bar and 298 K, as well as the record Xe capture capability from the nuclear reprocessing off-gas. Our work not only provides a benchmark Xe adsorbent but proposes a new route to construct smart materials for efficient separations.

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

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.

Molecular Sieving of Acetylene from Ethylene in a Rigid Ultra-microporous Metal Organic Framework.

Rigid molecular sieving materials are the ideal candidates for gas separation (e. g., C2 H2 /C2 H4 ) due to their ultrahigh adsorption selectivity and the absence of gas co-adsorption. However, the absolute molecular sieving effect for C2 H2 /C2 H4 separation has rarely been realized because of their similar physicochemical properties. Herein, we demonstrate the absolute molecular sieving of C2 H2 from C2 H4 by a rigid ultra-microporous metal-organic framework (F-PYMO-Cu) with 1D regular channels (pore size of ca. 3.4 Å). F-PYMO-Cu exhibited moderate acetylene uptake (35.5 cm3 /cm3 ), but very low ethylene uptake (0.55 cm3 /cm3 ) at 298 K and 1 bar, yielding the second highest C2 H2 /C2 H4 uptake ratio of 63.6 up to now. One-step C2 H4 production from a binary mixture of C2 H2 /C2 H4 and a ternary mixture of C2 H2 /CO2 /C2 H4 at 298 K was achieved and verified by dynamic breakthrough experiments. Coupled with excellent thermal and water stability, F-PYMO-Cu could be a promising candidate for industrial C2 separation tasks.

Tuning the Selectivity between C2H2 and CO2 in Molecular Porous Materials.

A combined experimental and theoretical study of C2H2 and CO2 adsorption and separation was performed in two isostructural molecular porous materials (MPMs): MPM-1-Cl ([Cu2(adenine)4Cl2]Cl2) and MPM-1-TIFSIX ([Cu2(adenine)4(TiF6)2]). It was revealed that MPM-1-Cl displayed higher low-pressure uptake, isosteric heat of adsorption (Qst), and selectivity for C2H2 than CO2, whereas the opposite was observed for MPM-1-TIFSIX. While MPM-1-Cl contains only one type of accessible channel, which has a greater preference toward C2H2, MPM-1-TIFSIX contains three distinct accessible channels, one of which is a confined region between two large channels that represents the primary binding site for both adsorbates. According to molecular simulations, the initial adsorption site in MPM-1-TIFSIX interacts more strongly with CO2 than C2H2, thus explaining the inversion of adsorbate selectivity relative to MPM-1-Cl.

A MOF-based Ultra-Strong Acetylene Nano-trap for Highly Efficient C2 H2 /CO2 Separation.

Porous materials with open metal sites have been investigated to separate various gas mixtures. However, open metal sites show the limitation in the separation of some challenging gas mixtures, such as C2 H2 /CO2 . Herein, we propose a new type of ultra-strong C2 H2 nano-trap based on multiple binding interactions to efficiently capture C2 H2 molecules and separate C2 H2 /CO2 mixture. The ultra-strong acetylene nano-trap shows a benchmark Qst of 79.1 kJ mol-1 for C2 H2 , a record high pure C2 H2 uptake of 2.54 mmol g-1 at 1×10-2  bar, and the highest C2 H2 /CO2 selectivity (53.6), making it as a new benchmark material for the capture of C2 H2 and the separation of C2 H2 /CO2 . The locations of C2 H2 molecules within the MOF-based nanotrap have been visualized by the in situ single-crystal X-ray diffraction studies, which also identify the multiple binding sites accountable for the strong interactions with C2 H2 .

Nanospace Engineering of Metal-Organic Frameworks through Dynamic Spacer Installation of Multifunctionalities for Efficient Separation of Ethane from Ethane/Ethylene Mixtures.

Herein, a dynamic spacer installation (DSI) strategy has been implemented to construct a series of multifunctional metal-organic frameworks (MOFs), LIFM-61/31/62/63, with optimized pore space and pore environment for ethane/ethylene separation. In this respect, a series of linear dicarboxylic acids were deliberately installed in the prototype MOF, LIFM-28, leading to a dramatically increased pore volume (from 0.41 to 0.82 cm3 g-1 ) and reduced pore size (from 11.1×11.1 Å2 to 5.6×5.6 Å2 ). The increased pore volume endows the multifunctional MOFs with much higher ethane adsorption capacity, especially for LIFM-63 (4.8 mmol g-1 ), representing nearly three times as much ethane as the prototypical counterpart (1.7 mmol g-1 ) at 273 K and 1 bar. Meanwhile, the reduced pore size imparts enhanced ethane/ethylene selectivity of the multifunctional MOFs. Theoretical calculations and dynamic breakthrough experiments confirm that the DSI is a promising approach for the rational design of multifunctional MOFs for this challenging task.

Amino-Functionalised Hybrid Ultramicroporous Materials that Enable Single-Step Ethylene Purification from a Ternary Mixture.

Pyrazine-linked hybrid ultramicroporous (pore size <7 Å) materials (HUMs) offer benchmark performance for trace carbon capture thanks to strong selectivity for CO2 over small gas molecules, including light hydrocarbons. That the prototypal pyrazine-linked HUMs are amenable to crystal engineering has enabled second generation HUMs to supersede the performance of the parent HUM, SIFSIX-3-Zn, mainly through substitution of the metal and/or the inorganic pillar. Herein, we report that two isostructural aminopyrazine-linked HUMs, MFSIX-17-Ni (17=aminopyrazine; M=Si, Ti), which we had anticipated would offer even stronger affinity for CO2 than their pyrazine analogs, unexpectedly exhibit reduced CO2 affinity but enhanced C2 H2 affinity. MFSIX-17-Ni are consequently the first physisorbents that enable single-step production of polymer-grade ethylene (>99.95 % for SIFSIX-17-Ni) from a ternary equimolar mixture of ethylene, acetylene and CO2 thanks to coadsorption of the latter two gases. We attribute this performance to the very different binding sites in MFSIX-17-Ni versus SIFSIX-3-Zn.

A Metal-Organic Framework Based Methane Nano-trap for the Capture of Coal-Mine Methane.

As a major greenhouse gas, methane, which is directly vented from the coal-mine to the atmosphere, has not yet drawn sufficient attention. To address this problem, we report a methane nano-trap that features oppositely adjacent open metal sites and dense alkyl groups in a metal-organic framework (MOF). The alkyl MOF-based methane nano-trap exhibits a record-high methane uptake and CH4 /N2 selectivity at 298 K and 1 bar. The methane molecules trapped within the alkyl MOF were crystalographically identified by single-crystal X-ray diffraction experiments, which in combination with molecular simulation studies unveiled the methane adsorption mechanism within the MOF-based nano-trap. The IAST calculations and the breakthrough experiments revealed that the alkyl MOF-based methane nano-trap is a new benchmark for CH4 /N2 separation, thereby providing a new perspective for capturing methane from coal-mine methane to recover fuel and reduce greenhouse gas emissions.

Robust Microporous Metal-Organic Frameworks for Highly Efficient and Simultaneous Removal of Propyne and Propadiene from Propylene.

Simultaneous removal of trace amounts of propyne and propadiene from propylene is an important but challenging industrial process. We report herein a class of microporous metal-organic frameworks (NKMOF-1-M) with exceptional water stability and remarkably high uptakes for both propyne and propadiene at low pressures. NKMOF-1-M separated a ternary propyne/propadiene/propylene (0.5 : 0.5 : 99.0) mixture with the highest reported selectivity for the production of polymer-grade propylene (99.996 %) at ambient temperature, as attributed to its strong binding affinity for propyne and propadiene over propylene. Moreover, we were able to visualize propyne and propadiene molecules in the single-crystal structure of NKMOF-1-M through a convenient approach under ambient conditions, which helped to precisely understand the binding sites and affinity for propyne and propadiene. These results provide important guidance on using ultramicroporous MOFs as physisorbent materials.

Simulations of hydrogen, carbon dioxide, and small hydrocarbon sorption in a nitrogen-rich rht-metal-organic framework.

Grand canonical Monte Carlo (GCMC) simulations of gas sorption were performed in Cu-TDPAH, also known as rht-MOF-9, hereafter [1], a metal-organic framework (MOF) with rht topology consisting of Cu2+ ions coordinated to 2,5,8-tris(3,5-dicarboxyphenylamino)-1,3,4,6,7,9,9b-heptaazaphenalene (TDPAH) ligands. This MOF is notable for the presence of open-metal copper sites and high nitrogen content on the linkers. [1] Exhibits one of the highest experimental H2 uptakes at 77 K/1 atm within the extant rht-MOF family (ca. 2.72 wt%) and also has strong affinity for CO2 (5.83 mmol g-1 at 298 K/1 atm). Our simulations, which include explicit many-body polarization interactions, accurately modeled macroscopic thermodynamic properties (e.g., sorption isotherms and isosteric heats of adsorption (Qst)) as well as the binding sites for H2, CO2, CH4, C2H2, C2H4, and C2H6 in the MOF. Four different binding sites were observed through analysis of the radial distribution function (g(r)) about the two chemically distinct Cu2+ ions, simulated annealing calculations, and examination of the three-dimensional histogram showing the sites of occupancy: (1) at the Cu2+ ion facing toward the center of the linker (CuL), (2) at the Cu2+ ion facing away from the center of linker (CuC), (3) nestled between three [Cu2(O2CR)4] units in the corner of the truncated tetrahedral (T-Td) cage and (4) straddling the copper nuclei parallel to the axis of the Cu-Cu bond within the T-Td cage. The low-loading (initial) binding site in the MOF is highly sensitive to the partial charges of the Cu2+ ions that were used for parametrization. It was discovered that most sorbates prefer to sorb onto or near the Cu2+ ions that exhibit the greater partial positive charge (i.e., at site 1). The simulated H2 and CO2 sorption results obtained using a polarizable potential for the respective sorbates are in good agreement with the corresponding experimental data, especially near ambient pressure. Simulations of gas sorption were also performed in [1] using nonpolarizable potentials for the individual sorbates; these include potentials from the TraPPE force field for most sorbates.

Robust Ultramicroporous Metal-Organic Frameworks with Benchmark Affinity for Acetylene.

Highly selective separation and/or purification of acetylene from various gas mixtures is a relevant and difficult challenge that currently requires costly and energy-intensive chemisorption processes. Two ultramicroporous metal-organic framework physisorbents, NKMOF-1-M (M=Cu or Ni), offer high hydrolytic stability and benchmark selectivity towards acetylene versus several gases at ambient temperature. The performance of NKMOF-1-M is attributed to their exceptional acetylene binding affinity as revealed by modelling and several experimental studies: in situ single-crystal X-ray diffraction, FTIR, and gas mixture breakthrough tests. NKMOF-1-M exhibit better low-pressure uptake than existing physisorbents and possesses the highest selectivities yet reported for C2 H2 /CO2 and C2 H2 /CH4 . The performance of NKMOF-1-M is not driven by the same mechanism as current benchmark physisorbents that rely on pore walls lined by inorganic anions.

Efficient CO2 Removal for Ultra-Pure CO Production by Two Hybrid Ultramicroporous Materials.

Removal of CO2 from CO gas mixtures is a necessary but challenging step during production of ultra-pure CO as processed from either steam reforming of hydrocarbons or CO2 reduction. Herein, two hybrid ultramicroporous materials (HUMs), SIFSIX-3-Ni and TIFSIX-2-Cu-i, which are known to exhibit strong affinity for CO2 , were examined with respect to their performance for this separation. The single-gas CO sorption isotherms of these HUMs were measured for the first time and are indicative of weak affinity for CO and benchmark CO2 /CO selectivity (>4000 for SIFSIX-3-Ni). This prompted us to conduct dynamic breakthrough experiments and compare performance with other porous materials. Ultra-pure CO (99.99 %) was thereby obtained from CO gas mixtures containing both trace (1 %) and bulk (50 %) levels of CO2 in a one-step physisorption-based separation process.

Investigating gas sorption in an rht-metal-organic framework with 1,2,3-triazole groups.

Simulations of CO2 and H2 sorption were performed in an rht-metal-organic framework (MOF) that consists of Cu2+ ions coordinated to 5,5',5''-(4,4',4''-(benzene-1,3,5-triyl)tris(1H-1,2,3-triazole-4,1-diyl))triisophthalate (BTTI) linkers; it is referred to as Cu-BTTI herein. This MOF was previously synthesized and reported by three different experimental groups [Zhao et al., Sci. Rep., 2013, 3, 1149; Schröder et al., Chem. Sci., 2013, 4, 1731-1736; Hupp et al., Energy Environ. Sci., 2013, 6, 1158-1163]. This MOF is notable for the presence of open-metal sites and nitrogen-rich regions through the copper paddlewheel ([Cu2(O2CR)4]) clusters and 1,2,3-triazole groups, respectively, which allows this material to display remarkable CO2 and H2 sorption properties. All three groups report distinct experimental and theoretical gas sorption results for the MOF. In contrast to the force fields utilized in the aforementioned studies, our simulations include explicit many-body polarization interactions, which was important to reproduce sorption onto the open-metal sites. Simulations using polarizable potentials for the MOF and sorbates generated sorption isotherms and isosteric heat of adsorption (Qst) values that are outstanding agreement with the corresponding experimental data for all three groups; this is in contrast to the theoretical results presented in the respective original references. The simulations carried out in the previous studies often looked reasonable but they missed a key feature of the sorption process that lead to unreliable results. Analysis of the radial distribution function (g(r)) about the open-metal sites and examination of the modeled structure reveal that the CO2 and H2 molecules prefer to sorb onto two unique types of Cu2+ ions that exhibit the highest partial positive charges. Sorption was also observed within the corners of the truncated tetrahedral (T-Td) cages and onto the 1,2,3-triazole groups of the linkers for both sorbates. Overall, this study demonstrates how utilizing a classical polarizable force field led to the reproduction of experimental observables and allowed for an accurate description of the sorption mechanism in this MOF that is an important member of the rht-MOF family.

Predictive models of gas sorption in a metal-organic framework with open-metal sites and small pore sizes.

Simulations of CO2 and H2 sorption were performed in UTSA-20, a metal-organic framework (MOF) having zyg topology and composed of Cu2+ ions coordinated to 3,3',3'',5,5',5''-benzene-1,3,5-triyl-hexabenzoate (BHB) linkers. Previous experimental studies have shown that this MOF displays remarkable CO2 sorption properties and exhibits one of the highest gravimetric H2 uptakes at 77 K/1.0 atm (2.9 wt%) [Z. Guo, et al. Angew. Chem., Int. Ed., 2011, 50, 3178-3181]. For both sorbates, the simulations were executed with the inclusion of explicit many-body polarization interactions, which was necessary to reproduce sorption onto the open-metal sites. Non-polarizable potentials were also utilized for simulations of CO2 sorption as a control. The simulated excess sorption isotherms for both CO2 and H2 are in very good agreement with the corresponding experimental data over a wide range of temperatures and pressures, thus demonstrating the accuracy and predictive power of the polarizable potentials used herein. The theoretical isosteric heat of adsorption (Qst) values are also in good agreement with the newly reported experimental Qst values for the respective sorbates in UTSA-20. Sorption onto the more positively charged Cu2+ ion of the [Cu2(O2CR)4] cluster was observed for both CO2 and H2. However, a binding site with energetics comparable to that for an open-metal site was also discovered for both sorbates. A radial distribution function (g(r)) analysis about the preferential Cu2+ ions for CO2 and H2 revealed that both sorbates display different trends for the relative occupancy about such sites upon increasing/decreasing the pressure in the MOF. Overall, this study provides insights into the CO2 and H2 sorption mechanisms in this MOF containing open-metal sites and small pore sizes for the first time through a classical polarizable force field.

The rotational dynamics of H2 adsorbed in covalent organic frameworks.

A combined inelastic neutron scattering (INS) and theoretical study was carried out on H2 adsorbed in two covalent organic framework (COF) materials: COF-1 and COF-102. These COFs are synthesized from self-condensation reactions of 1,4-benzenediboronic acid (BDBA) and tetra(4-(dihydroxy)borylphenyl)methane (TBPM) molecules, respectively. Molecular simulations of H2 adsorption in COF-1 revealed that the H2 molecules occupy the region between two eclipsed layers of the COF. The most favorable H2 binding site in COF-1 is located between two B3O3 clusters of the eclipsed layers. Two distinct H2 binding sites were identified in COF-102 from the simulations: the B3O3 clusters and the phenyl rings of the tetraphenylmethyl units. Two-dimensional quantum rotation calculations for H2 adsorbed at the considered sites in both COFs resulted in rotational transitions that are in good agreement with those that appear in the corresponding INS spectra. Such calculations were important for interpreting the INS spectra in these materials. Calculation of the rotational potential energy surface for H2 bound at the most favorable adsorption site in COF-1 and COF-102 revealed unusually high rotational barriers that are attributed to the nature of the B3O3 rings. The values for these barriers to rotation are greater than or comparable to those observed in some metal-organic frameworks (MOFs) that possess open-metal sites. This study demonstrates the power of using INS experiments in conjunction with theoretical calculations to gain valuable insights into the nature of the binding sites and, for the first time, the rotational dynamics of H2 adsorbed in COFs.