Steering diffusion selectivity of chemical isomers within aligned nanochannels of metal-organic framework thin film

Steering diffusion selectivity of chemical isomers within aligned nanochannels of metal-organic framework thin film | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Steering diffusion selectivity of chemical isomers within aligned nanochannels of metal-organic framework thin film Ritesh Haldar, Tanmoy Maity, Susmita Sarkar, Susmita Kundu, Suvendu Panda, and 4 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4046811/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 08 Nov, 2024 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract The movement of molecules (i.e. diffusion) within angstrom-scale pores of porous materials such as metal-organic frameworks (MOFs) and zeolites is influenced by multiple complex factors that can be challenging to assess and manipulate. Nevertheless, understanding and controlling this diffusion phenomenon is crucial for advancing energy-economic membrane-based chemical separation technologies, as well as for heterogeneous catalysis and sensing applications. Through precise assessment of the factors influencing diffusion within a porous metal-organic framework (MOF) thin film, we have developed a chemical strategy to manipulate and reverse chemical isomer diffusion selectivity. In the process of cognizing the molecular diffusion within oriented, angstrom-scale channels of MOF thin film, we have unveiled a dynamic chemical interaction between the adsorbate (chemical isomers) and the MOF using a combination of kinetic mass uptake experiments and molecular simulation. Leveraging the dynamic chemical interactions, we have reversed the haloalkane (positional) isomer diffusion selectivity, forging a novel chemical pathway to elevate the overall efficacy of membrane-based chemical separation and selective catalytic reactions. Physical sciences/Chemistry/Materials chemistry/Metal–organic frameworks Physical sciences/Materials science/Materials for energy and catalysis/Metal–organic frameworks Figures Figure 1 Figure 2 Figure 3 Figure 4 Introduction Nanoporous materials such as zeolites, 1 metal-organic frameworks (MOFs) 2,3 and covalent-organic frameworks (COFs) 4 hold substantial importance in applications involving chemical storage, separation and catalytic conversions. The significance of these nanoporous materials has grown significantly; 5,6 especially since they offer sustainable, energy economic and low carbon footprint technologies, e.g membrane based chemical separation. 7-9 In these practical contexts, the prevalent factor influencing efficiency is molecular diffusion. 8,10-12 The movement of the molecules through chemically functionalized channels of the nanoporous materials is influenced by various factors, including chemical interactions (adsorbate-adsorbent), concentration gradient, channel size and shape. 12 Occasionally, using imaging 13 and spectroscopic techniques 14 it has been possible to visualize the molecular diffusion path. 12 However, modulation of diffusion and subsequent manipulation of material properties pose significantly greater challenges. Among the nanoporous materials, MOFs are crystalline, versatile topology, high porosity (surface area > 7000 m 2 /g) material and well-known for chemical storage, separation, 15,16 sensing 17 and catalysis 18,19 applications. A great number of literatures reflect applicability of MOFs as functional nanoporous material, and also the successful chemical design strategies that have improved their performance. Notably, while many of the synthesized MOFs excel in adsorption-based separation (i.e. at equilibrium), 15 relatively a few serve as membranes (~1 % of the all known MOFs), 9,20 relying on differences in diffusivity for separation. The reason of relatively fewer selected MOFs for membrane based separation is (apart from processibility issues) that a predictive design of pore geometry and functionality for diffusion control is far more challenging than the adsorption process. 21,22 For the heterogeneous catalysis too, role of substrate diffusivity is not well investigated. One mechanism of overcoming this challenge is to develop a computational screening approach. By simulating molecular diffusion within MOF pores, not only may the sampling volume can be accelerated, but it can also offer insights into the interactions between the adsorbate and MOF (thermodynamic and kinetic). 23-25 Utilizing knowledge of diffusivity and interactions, it becomes feasible to tailor porous materials to exhibit targeted molecular diffusion, facilitating chemical separation and catalysis. While the computational screening approaches for MOF-membrane design have received a significant interest, 26,27 experimental manipulation of diffusivity has remained challenging. Recent experimental efforts, such as downsizing MOF crystallite size, morphology control, 28 controlling nanochannel orientation 29-31 and employing novel heterostructure design 32-36 improve molecular diffusivity, however do not predictively tune the diffusivity. It is evident that for controlling molecular diffusion, a comprehensive strategy to assess the thermodynamics and kinetics is much needed. In this communication, we have employed a strategy incorporating both precise measurement of mass uptake kinetics and molecular dynamic (MD) simulation. This approach was applied within a specifically designed and functionalized nanochannel of (pillared-layer) MOF thin film to understand and regulate molecular diffusion of chemical isomers. Our findings confirm that nanochannel orientation, distribution of chemical functionality on the pore surface and framework dynamics work in tandem to regulate molecular diffusion rate and direction. Leveraging these insights, we establish an adsorbate-MOF “dynamic chemical interaction”. The unveiled dynamic interactions profoundly influence molecular diffusion; as we evidence, certain linker-adsorbate interactions can enhance or hinder diffusion on the basis of framework dynamics. In the following discussion, we have illustrated a chemical strategy to implement the “dynamic chemical interaction” and utilizing this we have achieved an unprecedented reversal of diffusion selectivity for 1 and 2-bromopropane (1BP and 2BP) positional isomers in the nanoporous MOF thin film (Figure 1). Results The various factors governing molecular diffusion in MOFs include: i) pore window and cavity size, ii) orientation of nanochannels, iii) distribution of chemical functionality on the pore surface, iv) adsorption enthalpy and v) linker/framework flexibility. 12 Although these factors are well recognized, combined effect of these are challenging to perceive and implement. We have considered each of these factors to design a MOF thin film and study the diffusion selectivity of 1BP and 2BP isomers. The halogenated alkane isomers are commercially important chemical feedstocks (for lubricants, pesticides, PVC production) 37 and very few studies highlighted the possibility of adsorptive separation of these isomers. 38 We chose the brominated isomers as a proof of concept to demonstrate the potential of “dynamic chemical interaction”. Firstly, we outline the design strategy of the oriented nanochannel MOF structure and evaluate the diffusion selectivity for the isomers. Subsequently, we establish the dynamic chemical interactions in the MOF thin film and apply those to reverse isomer diffusion selectivity. The selected nanoporous system is a pillared-layer type MOF 39 (Figure 2a); a Cu 2+ -dimeric paddle-wheel node is linked by bdc (1,4-benzenedicarboxylic acid) to form a square-grid type 2D layer. This 2D layer is pillared (along [001] axis) by a azbpy (4,4'-azobipyridyl) to form a PCU topology Cu(bdc)(azbpy) MOF having two distinct pore windows. The window dimensions are 7.3 Å × 4.3 Å (along [001]) and 9.7 Å × 6.9 Å, calculated by adding van der Waals surface in a periodic density functional theory (DFT) optimized structure (at 0 K). To realize the MOF pore window orientation, as illustrated in Figure 2a, we have used a layer-by-layer, liquid-phase epitaxial growth technique. 40,41 A self-assembled monolayer (-OH terminated) functionalized Au surface was alternately exposed to Cu(CH 3 COO) 2 and mixture of bdc and azbpy linkers solution to grow the surface anchored MOF or SURMOF (described elsewhere). 39 Out-of-plane x-ray diffraction (XRD) pattern exhibited diffraction peaks related to (001) plane, and in-plane pattern exhibited diffraction peaks related to (100) and (010) planes (Figure 2b). This confirmed a [001] oriented SURMOF, as illustrated in Figure 2a. The scanning electron microscopy images confirmed a monolithic film growth, as illustrated in Figure 2c. Note that the pore window dimensions are large enough to allow diffusion of the bromopropane isomers (1BP = 8 Å × 4.7 Å; 2BP = 6.9 Å × 6.6 Å, calculated by adding van der Waals surface). For the [001] oriented SURMOF, the Cu(bdc) planes are exposed to the surface. Hence, we anticipated that the geometry based adsorption and diffusion selectivity for the bromopropane isomers will be regulated by the 7.3 Å × 4.3 Å sized pore window. To measure the adsorption and diffusion selectivities, we have used quartz crystal microbalance (QCM) technique. 39,42 In this method, SURMOF is grown on Au-coated quartz crystal sensor and mounted inside a fluidic cell. A constant flow of saturated solvent vapor through the fluidic cell allow measuring the mass uptake (mass is calculated using Sauerbrey equation, see experimental section). For the Cu(bdc)(azbpy) thin film, the mass uptake profiles for the isomers are shown in Figure 2c and Figure S1. We describe the uptake profiles using an exponential decay function 43 : One possible explanation of this opposing trend of adsorption and diffusion is following: higher adsorption is due to stronger adsorbate-adsorbent interaction, which reduces the molecular mobility. 51 To appraise this observation, MD simulation was performed on the most probable conformation obtained from AIMD simulation of the periodic unit of Cu(bdc)(azbpy) at 300 K (see supporting information). At first we have excluded framework dynamics, because we anticipated only adsorbent-adsorbate interaction-driven diffusivity trends. As illustrated in Figure 3a and S2, the diffusion selectivity along [001] axis was found to be 1BP>2BP (estimated from mean square displacement, MSD, See Table S1). This is in contrary to the experimental observation and also implies that only adsorbate-adsorbent interaction strength is not the governing factor. In the next step, we have introduced framework dynamics and performed a similar simulation as done for rigid framework. Comparison of the MSD profiles indicated a selectivity trend of 2BP>1BP, in accordance to the experimental data. Assessment of the effective close proximity interactions (g(r)) between isomers and host framework revealed that the most influential chemical group in the framework is the bdc (Figure S3). The faster diffusion of 2BP in comparison to 1BP can be rationalized based on following order of interactions: 2BP – bdc > 1BP – bdc, 1BP – azbpy > 2BP – azbpy. Analysis of the specific Br – MOF interactions reveals that there is a stronger specific Br – bdc i.e. Br– π interaction for 2BP than 1BP (Figure 3b and S4). The specific Br – π(bdc) interaction is further validated by performing ab initio MD (AIMD) simulation and analyzing the trajectory during the timespan of intrapore molecular movement (see experimental section, Figure 3c; note that the diffusion selectivity observed in this simulation is same as the one observed in MD of flexible MOF, see Figure S5a). Stronger interaction with bdc accelerates diffusion, while stronger interaction with the azbpy decelerates diffusion. These observations underscore that in addition to the chemical interactions, the framework dynamics also contribute to the overall driving force. We term this effect as “dynamic chemical interaction”, a phenomenon validated in subsequent sections. Drawing from the MD simulation insights, we have in silico reconfigured the pore windows along [001] orientation; i.e. substituting the bdc linker with a Br 2 -bdc (2,5-dibromobenzene-1,4-dicarboxylic acid) linker. This intuitive chemical functionality transformation changes not only the specific chemical interactions between the chemical isomer and the bdc linkers but also changes the framework dynamics. The change in the framework dynamics of the bdc linkers is also captured in the most probable configuration obtained during AIMD simulation of the Cu(bdc)(azbpy) and Cu(Br 2 -bdc)(azbpy) at 300 K (Figure S5). We have performed a similar set of MD simulation for Cu(Br 2 -bdc)(azbpy), as done for Cu(bdc)(azbpy) ( vide supra ). As evident from the Figure 3a and S6, the MSD values obtained appear very different, than those observed for Cu(bdc)(azbpy). Mainly, 1BP diffusion is found to be relatively faster. Inspection of the close proximity interactions revealed following order: 1BP – Br 2 -bdc > 2BP – Br 2 -bdc and 1BP – azbpy < 2BP – azbpy (Figure S7-8). This reverse order of interactions reverses the diffusion selectivity. We attribute this reversal to the proposed dynamic chemical interaction, as the diffusion is effected by chemical interaction and framework dynamics. Next, we have experimentally attempted to execute the in silico findings. Attempts to synthesize an isostructural, oriented Cu(Br 2 -bdc)(azbpy) thin film akin to Cu(bdc)(azbpy) proved unsuccessful (Figure S9). However, a successful strategy emerged through a mixed-linker approach, 21,52-55 yielding Cu(Br 2 -bdc) x (bdc) 1-x (azbpy) (x = 0.012, 0.026 and 0.058) thin films (x was quantified by (reverse phase HPLC, see Figure S10). These mixed-linker MOF thin films maintained high crystallinity, preferred [001] orientation and exhibited homogenous surface coverage, as evidenced by the out-of-plane XRD, SEM images and elemental analysis and mapping ((Figure 4a-c, S11-14). Subsequently, we conducted 1BP and 2BP vapor uptake experiments using QCM for these mixed-linker MOF thin films (Figure S15). Similar to the case of Cu(bdc)(azbpy), we have calculated the saturation adsorption amount/pore and D . The Br 2 -bdc % vs D and adsorption amount/pore plots are presented in Figure 4d-e. Across all the mixed-linker thin films, the saturation adsorption amounts are higher for 1BP, resembling the trend observed in the parent structure Cu(bdc)(azbpy). Moreover, with increasing % of the Br 2 -bdc, adsorption amount decreased for both the isomers. This reduction in adsorption can be attributed to the steric effect introduced by the bulky –Br atoms. Surprisingly, a reversal in D is observed for Cu(Br 2 -bdc) 0.058 (bdc) 0.942 (azbpy) thin film. In comparison to the parent structure, D value for 2BP decreased ca. 8x and for 1BP increased ca . 0.5x. The experimental observation may be correlated to the in silico experiment; however several other factors merit consideration: i) inhomogeneous mixing of the linkers leading to segregated crystalline phases, ii) the presence of structural defects, and iii) changes in crystalline domain sizes. These three factors are discounted based on the following experimental observations: a) Out-of-plane XRD patterns of the mixed-linker thin films did not reveal new diffraction peaks, confirming that a new crystalline phase of Cu + (Br 2 -bdc) +(azbpy) did not form. However, when the Br 2 -bdc % increased to 17, new diffraction peaks emerged (Figure S16). This confirmed that mixed-linker phase is feasible only for low % of Br 2 -bdc. b) IRRA spectra of the mixed-linker and parent Cu(bdc)(azbpy) confirmed that the asymmetric and symmetric –COO stretching vibrations of the paddle-wheel node (1630 and 1388 cm -1 , respectively) remained unaltered (Figure S17). This underscores the absence of new crystalline phase. In the case of 17% Br 2 -bdc, the asymmetric and symmetric –COO stretching vibrations are different than those of the mixed-linker MOFs, consistent with the out-of-plane XRD patterns (Figure S17). c) Comparison of the (001) diffraction peak full width at half maxima for the mixed-linker and parent structure confirmed very similar crystalline domain sizes (30-34 nm) (Figure S18). d) SEM images and elemental mapping of the mixed-linker film confirmed the homogenous coverage and uniform distribution of the Br 2 -bdc functionality (Figure 4c). Based on these observations, the reversed selectivity can be attributed to the chemical interactions which are observed for the in silico designed Cu(Br 2 -bdc)(azbpy). Note that a higher concentration of Br 2 -bdc in the Cu(bdc)(azbpy) may have more prominent effect on the diffusivity (i.e. selectivity); however those structures could not be realized experimentally. Conclusion The chosen pillared-layer type MOF thin film exhibits distinct pore windows and functionality along the concentration gradient (i.e. [001]). Using these oriented nanochannels, we have concluded that diffusivity of two chemical isomers (1BP and 2BP) can be precisely manipulated and reversed using chemical design principles. To arrive at this conclusion, we have compared the observed chemical isomer diffusivities within a pillared-layer MOF thin film with those obtained from MD simulation. It is evident that diffusion has an intriguing dependence on the framework dynamics, while specific chemical interactions (like Br-π interaction) are also substantially important. We have hypothesized that the framework dynamics and chemical interactions as tool to predictively alter the chemical isomer diffusivity. Initially in silico and later by using a mixed-linker approach we have shown that diffusivity of isomers can be reversed. To ensure that the experimental findings are exclusively attributed to the dynamic chemical interaction, we have performed careful characterizations of the thin films. The experimental observations and the hypothesized chemical strategy are unprecedented. Although this predictive alteration of diffusion is currently showcased for a pair of haloalkane isomer within pillared-layer type MOF, it’s important to note that the chemical design route transcends the boundaries of specific isomers and porous materials. In the future, the proposed methodology will be implemented to improve separation efficiency of the chemical isomers which are more challenging to perform using conventional distillation technique. Material Cu(CH 3 COO) 2 ·H 2 O, 1,4-benzenedicarboxylic acid (bdc), 2,5-dibromobenzene-1,4-dicarboxylic acid (Br 2 -bdc), anhydrous n-bromopropane (1BP) and iso-bromopropane (2BP) were purchased from Sigma-Aldrich. All chemicals were used as received without further purification. QCM Sensors (5MHz) were purchased from openQCM. Methods: Synthesis of 4,4'-Azobipyridine : 4,4'-azobipyridine was synthesized following a reported method. 56 Synthesis of pillared-layer MOF thin films on QCM sensor : 5 MHz (Au coated) QCM-sensors were dipped in an ethanolic solution (20 mM) of 11-mercapto-1-undecanol (MUD) for 24 hours to obtain –OH functionalized surface. These substrates were then thoroughly washed with absolute ethanol (99.99%), dried and used for thin films synthesis. The MOF thin films were prepared on those functionalized substrate via a well-known layer-by-layer (lbl) liquid-phase epitaxial (LPE) method. 57 The method consists of four steps to complete a cycle at 60 ºC as: i) dipped in 1 mM copper acetate ethanol solution for 15 minutes, ii) drained the metal solution and washed with fresh ethanol, iii) dipped in 0.2 mM linker solution (mixture of two linkers) in ethanol for 30 minutes and iv) drained the linker solution and washed with fresh ethanol. MOF thin films with varying doping percentage were prepared by varying the linker solution in different Br 2 BDC proportions. 4,4'-azobipyridine is the only pillar linker used with either 1,4-Benzene dicarboxylic acid linker or mixture of two dicarboxylic acids (1,4-Benzene dicarboxylic acid and 2,5-dibromobenzene-1,4-dicarboxylic acid) for MOF thin films upto 60 cycles. Characterizations : Powder x-ray diffractometer (XRD) patterns of thin films were recorded on a Rigaku XDS 2000 diffractometer using nickel-filtered Cu K α radiation ( λ = 1.5418 Å) ranging from 5 to 20 ° at room temperature (voltage 40 kV, current 200 mA). Out-of plane PXRD was recorded in 2 θ / θ (step size 0.01, scan rate 0.2 º/s), in-plane in 2 θ / φ geometry with grazing incident angle ( ω ) at 0.5 º and step size of 0.12 with scan rate 0.1 º/s. Surface morphology of the MOF thin films were characterized using field emission scanning electron microscopy (FESEM), JEOL JSM-7200F instrument with a cold emission gun operating at 5 kV. Energy-Dispersive X-ray spectroscopy (EDS) elemental analysis and mapping were also done on the FESEM (at 15 kV). IRRA (Infrared Reflection Absorption) spectrum (4000–600 cm –1 ) was collected under vacuum using Bruker VERTEX 70v with 2 cm -1 resolution and with 128 scan rate. X-ray photoelectron spectroscopy (PHI versaProbe III) was performed for the MOF thin films under ultrahigh vacuum (10 -9 bar) environment. The adsorption (mass uptake) profiles were measured using a quartz crystal microbalance (QCM) from open QCM, Italy. Thickness for all the thin films was calculated using J.A. Wollam ellipsometer (alpha-SE). The data was fitted using a B-Spline model including surface roughness. Analytical reverse-phase (RP) HPLC was performed on an Agilent HPLC instrument using an Agilent zorbax SB-C3 (5 μm), 4.6×150 mm reverse-phase column at a flow rate of 0.9 mL/min using a linear gradient of solvent B in solvent A at 40 °C (solvent A = 0.1% TFA in H 2 O; solvent B = 0.08% TFA in acetonitrile). The 214 nm UV absorbance of the column eluent was monitored. During sample preparation, compounds were weighed out in their mentioned ratios and dissolved in 200µL of DMSO. From this stock solution, 5µL was taken and diluted with 60µL DMSO and 60µL of B solvent (B = 0.08% TFA in acetonitrile). Then 0.5 µL injected in HPLC for analysis. MOF thin films deposited on QCM substrate were dipped in 18 mM aqueous solution of Na 2 EDTA·2H 2 O (Na 2 EDTA = ethylenediaminetetraacetic acid disodium salt) to disintegrate the MOF structure and remove Cu 2+ from the solution. After pH adjustment to ~6, the clear aqueous solution (obtained by centrifugation) was taken for the (RP) HPLC analysis. QCM experiments : MOF thin films were activated at 65 °C at 0.1 mbar. Mass uptake experiments were carried out using a constant flow rate (50 sccm) of dry N 2 , passing through saturated solvent vapors (1 and 2BP). Analyses of uptake kinetics : Mass-frequency relationship for the QCM measurements is given by Sauerbrey equation; 42 Where n denotes the overtone order (n = 3, 5, and 7) and c is the mass sensitivity constant. For a 5 MHz crystal, c has value of 17.7 ng/cm 2 . We examine the data with the assumption of Fickian diffusion, that is, we assume a constant diffusivity, D , is independent of the vapor concentration. Where M t is the uptake (g) at time t , M sat is the uptake (g) at infinite time (i.e., at equilibrium), D has units of m 2 /s, and l is the film thickness. Following the Wöll and coworkers report, 43 the above equation can be expressed as following: D is calculated using the τ value, obtained by fitting equation 3. Molecular dynamics simulation : At first, the corresponding superstructure is generated from the unit cell of the Cu(bdc)(azbpy) MOF spanning along 3*3*6 dimensions. We have considered two situations with the superstructure framework extended as 3*3*6 (in x, y, z directions respectively) considering : I) high concentration gradient, i.e MOF thin film pores are almost empty (containing only one molecule of each of the alkanes, 1BP and 2BP in the framework), II) low concentration gradient, i.e. ~20% (of saturation amount) filled pores (including multiple molecules of each type of alkane at a time, i.e. 11 molecules of 1BP and 9 molecules of 2BP corresponding to the respective number of molecular uptakes at ~20% loading). Initially, in both the cases molecular dynamics simulation is performed by freezing the MOF (utilizing ‘freeze group’ utility installed in gromacs) as we anticipated only adsorbent-adsorbate interaction driven diffusivity trends. The partial charges over the atoms of MOF are obtained from the quantum calculations (see below) and the alkane molecules are modeled using charmm36 force field parameters. 58-60 Each of the simulation both in high and low concentration gradient for each of the haloalkane molecules are performed in gas phase. The entire system was packed in a rectangular box of dimension 3.26 × 3.26 × 9.54 nm 3 as per the resultant dimension of the superstructure. Further, the similar set of simulations was performed in flexible framework. The respective bond, angle and dihedral parameters of the MOF were obtained using obgmx tool and the partial charges were kept unaltered as the set of the previous simulations performed excluding framework dynamics were excluded. To realize the effect of bromine substitution in MOF on the haloalkane isomer selectivity, Cu(Br 2 -bdc)(azbpy) has been simulated under the condition of high concentration gradient, i.e MOF thin film pores are almost empty (containing only one molecule of each of the alkanes, 1BP and 2BP in the framework). The simulations in brominated MOF for each of the haloalkane were carried out in flexible framework arrangement where the partial charges of MOF were obtained from the similar quantum calculation (see below) and the bond, angle and dihedrals parameters from obgmx. The alkanes were modeled with charmm36 parameters as utilized before. The dimension of the simulation box was kept fixed corresponding to the similar dimension of the MOF superstructure build along the direction of 3*3*6 (corresponding to x, y and z directions respectively). Simulation method : Each of the simulation is performed using periodic boundary conditions (PBC) set in all three dimensions. Long-range electrostatic interactions were maintained employing the particle mesh Ewald (PME) method 61 with cubic interpolation. For the electrostatic interactions at short-range, the cut-off of 1.2 nm was employed. During freezed framework simulation of the Cu(bdc)(azbpy), the MOF dynamics was excluded using “ freeze group” utility of gromacs. Otherwise for the alkane molecules in the freezed system and the MOF along with alkanes in the flexible framework system, for constraining each the bonds involving hydrogen atoms, the LINCS algorithm 62 was applied. At first, the system was energy minimized with the steepest-decent algorithm followed by stepwise equilibration in seven successive steps with gradual increase of temperature (in an interval of 50 K starting from 50 K upto 300 K) of 100 ps each (with time step of 0.0005 ps). During equilibration, the average temperature was kept fixed at the corresponding temperatures by using V-rescale thermostat via coupling the MOF and the alkane molecules separately. Finally, the equilibrated system was subjected to NVT production run for 10 nanosecond. During production simulation also, the average temperature of 300 K was maintained with the help of same V-rescale thermostat. To execute all simulations GROMACS software of version 20x were utilized. The diffusion phenomenon of the haloalkane molecules were inspected by calculating mean square displacement (msd) utilizing the tool of “gmx msd” and the corresponding diffusion coefficient ( D ) were approximated. To understand the mode of chemical interactions of the haloalkane molecules with the different parts of the MOF pair correlation function of the alkane moieties (whole molecule, bromine atom and the Cα carbon of the alkane molecule linked to the bromine group) were measured with respect to the specific parts of the MOF (i.e. –N=N-, pyridyl and bdc). Ab initio Molecular Dynamic Simulation All AIMD simulations were run using CP2K software 63 (version 9.1) with PBE functional 64 and each MD time step of 0.5 fs at 300 K. The dimensions of the cell with periodic boundary conditions were 10.886 Å, 10.886 Å, and 15.9041 Å. The valence electrons of H, C, N, and O atoms were modelled with DZVP-GTH basis sets whereas DZVP-MOLOPT-SR-GTH basis set was employed for Br and Cu centers. The core electrons of all the atoms were modelled using GTH-PBE pseudopotentials. All NVT simulations employed Nose-Hoover chain thermostatting. 65-67 For the self-diffusion studies, NVT simulations were run for 50 ps. The analysis of the probability distribution of Br (2BP and 1BP) - C (bdc linker) distance involved data collected at an interval of 5 fs during the crossing of the molecule across the pore (1BP: 12.5 ps – 17.5 ps; 2BP: 25 ps – 29 ps) surrounded by the bdc molecules. The MSDs were computed with freud code. 68 The calculation of the diffusion constant was done by linear fitting of the MSD data (between 12.5-17.5ps for 1BP and 22-28ps for 2BP). Declarations Author contribution : T.M, R.H conceived the idea and planned the experiments, T. M did the synthesis, measurements and analysis with guidance from R.H, S.K and S.P helped with the characterizations, A.S and K.M helped with the HPLC measurements, S.S did the MD simulation with guidance from J.M, S.G did AIMD simulation, manuscript draft was prepared with the inputs from all the authors. Acknowledgement : R.H acknowledges the financial support from the Science and Engineering Research Board (SERB), Govt. of India (Project No: SRG/2022/000927), all the authors acknowledge the intramural funds at TIFR Hyderabad from the Department of Atomic Energy (DAE), India, under Project Identification Number RTI 4007. We are grateful to Prof. S. Balasubramanian (JNCASR, India) for a very helpful discussion on the MD simulation. References Li, Y. & Yu, J. Emerging applications of zeolites in catalysis, separation and host–guest assembly. Nature Reviews Materials 6 , 1156-1174 (2021). Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The Chemistry and Applications of Metal-Organic Frameworks. Science 341 , 1230444 (2013). Kitagawa, S., Kitaura, R. & Noro, S.-i. Functional Porous Coordination Polymers. Angewandte Chemie International Edition 43 , 2334-2375 (2004). Geng, K. et al. Covalent Organic Frameworks: Design, Synthesis, and Functions. Chemical Reviews 120 , 8814-8933 (2020). Kitagawa, S. Future Porous Materials. Accounts of Chemical Research 50 , 514-516 (2017). Foo, M. L., Matsuda, R. & Kitagawa, S. Functional Hybrid Porous Coordination Polymers. Chemistry of Materials 26 , 310-322 (2014). Sholl, D. S. & Lively, R. P. Seven chemical separations to change the world. Nature 532 , 435-437 (2016). Knebel, A. & Caro, J. Metal–organic frameworks and covalent organic frameworks as disruptive membrane materials for energy-efficient gas separation. Nature Nanotechnology 17 , 911-923 (2022). Qian, Q. et al. MOF-Based Membranes for Gas Separations. Chemical Reviews 120 , 8161-8266 (2020). Peng, P., Gao, X.-H., Yan, Z.-F. & Mintova, S. Diffusion and catalyst efficiency in hierarchical zeolite catalysts. National Science Review 7 , 1726-1742 (2020). Dong, B. et al. Deciphering nanoconfinement effects on molecular orientation and reaction intermediate by single molecule imaging. Nature Communications 10 , 4815 (2019). Sharp, C. H. et al. Nanoconfinement and mass transport in metal–organic frameworks. Chemical Society Reviews 50 , 11530-11558 (2021). Zürner, A., Kirstein, J., Döblinger, M., Bräuchle, C. & Bein, T. Visualizing single-molecule diffusion in mesoporous materials. Nature 450 , 705-708 (2007). Kärger, J. & Ruthven, D. M. Diffusion in nanoporous materials: fundamental principles, insights and challenges. New Journal of Chemistry 40 , 4027-4048 (2016). Li, J.-R., Kuppler, R. J. & Zhou, H.-C. Selective gas adsorption and separation in metal–organic frameworks. Chemical Society Reviews 38 , 1477-1504 (2009). Sumida, K. et al. Carbon Dioxide Capture in Metal–Organic Frameworks. Chemical Reviews 112 , 724-781 (2012). Lustig, W. P. et al. Metal–organic frameworks: functional luminescent and photonic materials for sensing applications. Chemical Society Reviews 46 , 3242-3285 (2017). Yang, D. & Gates, B. C. Catalysis by Metal Organic Frameworks: Perspective and Suggestions for Future Research. ACS Catalysis 9 , 1779-1798 (2019). Bavykina, A. et al. Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives. Chemical Reviews 120 , 8468-8535 (2020). Liu, G. et al. Eliminating lattice defects in metal–organic framework molecular-sieving membranes. Nature Materials 22 , 769-776 (2023). Yu, X.-J. et al. Liquid-Phase Epitaxial Growth of Highly Oriented and Multivariate Surface-Attached Metal–Organic Frameworks. Journal of the American Chemical Society 141 , 18984-18993 (2019). Li, S., Chung, Y. G., Simon, C. M. & Snurr, R. Q. High-Throughput Computational Screening of Multivariate Metal–Organic Frameworks (MTV-MOFs) for CO2 Capture. The Journal of Physical Chemistry Letters 8 , 6135-6141 (2017). Listyarini, R. V., Gamper, J. & Hofer, T. S. Storage and Diffusion of Carbon Dioxide in the Metal Organic Framework MOF-5─A Semi-empirical Molecular Dynamics Study. The Journal of Physical Chemistry B 127 , 9378-9389 (2023). Skoulidas, A. I. Molecular Dynamics Simulations of Gas Diffusion in Metal−Organic Frameworks: Argon in CuBTC. Journal of the American Chemical Society 126 , 1356-1357 (2004). Formalik, F., Shi, K., Joodaki, F., Wang, X. & Snurr, R. Q. Exploring the Structural, Dynamic, and Functional Properties of Metal-Organic Frameworks through Molecular Modeling. Advanced Functional Materials n/a , 2308130 Azar, A. N. V., Velioglu, S. & Keskin, S. Large-Scale Computational Screening of Metal Organic Framework (MOF) Membranes and MOF-Based Polymer Membranes for H2/N2 Separations. ACS Sustainable Chemistry & Engineering 7 , 9525-9536 (2019). Daglar, H. & Keskin, S. High-Throughput Screening of Metal Organic Frameworks as Fillers in Mixed Matrix Membranes for Flue Gas Separation. Advanced Theory and Simulations 2 , 1900109 (2019). Sikdar, N., Bhogra, M., Waghmare, Umesh V. & Maji, T. K. Oriented attachment growth of anisotropic meso/nanoscale MOFs: tunable surface area and CO2 separation. Journal of Materials Chemistry A 5 , 20959-20968 (2017). Malik, P. & Haldar, R. Accessing accelerated molecular diffusion by nanopore alignment in a MOF thin film. Molecular Systems Design & Engineering 7 , 873-877 (2022). Datta, S. J. et al. Rational design of mixed-matrix metal-organic framework membranes for molecular separations. Science 376 , 1080-1087 (2022). Wang, L. et al. Aligned Metal–Organic Framework Nanoplates in Mixed-Matrix Membranes for Highly Selective CO2/CH4 Separation. Advanced Materials Interfaces 10 , 2202524 (2023). Fan, H. et al. MOF-in-COF molecular sieving membrane for selective hydrogen separation. Nature Communications 12 , 38 (2021). Kwon, H. T., Jeong, H.-K., Lee, A. S., An, H. S. & Lee, J. S. Heteroepitaxially Grown Zeolitic Imidazolate Framework Membranes with Unprecedented Propylene/Propane Separation Performances. Journal of the American Chemical Society 137 , 12304-12311 (2015). Li, W. et al. Transformation of metal-organic frameworks for molecular sieving membranes. Nature Communications 7 , 11315 (2016). Song, Z. et al. Dual-Channel, Molecular-Sieving Core/Shell ZIF@MOF Architectures as Engineered Fillers in Hybrid Membranes for Highly Selective CO2 Separation. Nano Letters 17 , 6752-6758 (2017). Tonnah, R. K. et al. Bioinspired Angstrom-Scale Heterogeneous MOF-on-MOF Membrane for Osmotic Energy Harvesting. ACS Nano 17 , 12445-12457 (2023). Marshall, K. A. et al. in Ullmann's Encyclopedia of Industrial Chemistry 1-22. Hua, B. et al. Tuning the porosity of triangular supramolecular adsorbents for superior haloalkane isomer separations. Chemical Science 12 , 12286-12291 (2021). Maity, T. et al. Chemically routed interpore molecular diffusion in metal-organic framework thin films. Nature Communications 14 , 2212 (2023). Shekhah, O. et al. Step-by-Step Route for the Synthesis of Metal−Organic Frameworks. Journal of the American Chemical Society 129 , 15118-15119 (2007). Chen, D.-H., Gliemann, H. & Wöll, C. Layer-by-layer assembly of metal-organic framework thin films: Fabrication and advanced applications. Chemical Physics Reviews 4 (2023). Zybaylo, O. et al. A novel method to measure diffusion coefficients in porous metal–organic frameworks. Physical Chemistry Chemical Physics 12 , 8093-8098 (2010). Heinke, L., Gu, Z. & Wöll, C. The surface barrier phenomenon at the loading of metal-organic frameworks. Nature Communications 5 , 4562 (2014). Ling, Y. et al. A zinc(ii) metal–organic framework based on triazole and dicarboxylate ligands for selective adsorption of hexane isomers. Chemical Communications 47 , 7197-7199 (2011). Chen, B. et al. A Microporous Metal–Organic Framework for Gas-Chromatographic Separation of Alkanes. Angewandte Chemie International Edition 45 , 1390-1393 (2006). Henrique, A., Rodrigues, A. E. & Silva, J. A. C. Separation of Hexane Isomers in ZIF-8 by Fixed Bed Adsorption. Industrial & Engineering Chemistry Research 58 , 378-394 (2019). Xu, X., Cui, Q., Chen, H. & Huang, N. Carborane-Based Three-Dimensional Covalent Organic Frameworks. Journal of the American Chemical Society 145 , 24202-24209 (2023). Henrique, A. et al. Hexane isomers separation on an isoreticular series of microporous Zr carboxylate metal organic frameworks. Journal of Materials Chemistry A 8 , 17780-17789 (2020). Ferreira, A. F. P. et al. Sieving di-branched from mono-branched and linear alkanes using ZIF-8: experimental proof and theoretical explanation. Physical Chemistry Chemical Physics 15 , 8795-8804 (2013). Vlugt, T. J. H. et al. Adsorption of Linear and Branched Alkanes in the Zeolite Silicalite-1. Journal of the American Chemical Society 120 , 5599-5600 (1998). Krishna, R. & van Baten, J. M. Highlighting the Anti-Synergy between Adsorption and Diffusion in Cation-Exchanged Faujasite Zeolites. ACS Omega 7 , 13050-13056 (2022). Deng, H. et al. Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks. Science 327 , 846-850 (2010). Dong, Z., Sun, Y., Chu, J., Zhang, X. & Deng, H. Multivariate Metal–Organic Frameworks for Dialing-in the Binding and Programming the Release of Drug Molecules. Journal of the American Chemical Society 139 , 14209-14216 (2017). Ko, S. et al. Effect of Spatial Heterogeneity on the Unusual Uptake Behavior of Multivariate-Metal–Organic Frameworks. Journal of the American Chemical Society 145 , 3101-3107 (2023). Kong, X. et al. Mapping of Functional Groups in Metal-Organic Frameworks. Science 341 , 882-885 (2013). Launay, J. P., Tourrel-Pagis, M., Lipskier, J. F., Marvaud, V. & Joachim, C. Control of intramolecular electron transfer by a chemical reaction. The 4,4'-azopyridine/1,2-bis(4-pyridyl)hydrazine system. Inorganic Chemistry 30 , 1033-1038 (1991). Wannapaiboon, S. et al. Control of structural flexibility of layered-pillared metal-organic frameworks anchored at surfaces. Nature Communications 10 , 346 (2019). Huang, J. et al. CHARMM36m: an improved force field for folded and intrinsically disordered proteins. Nature Methods 14 , 71-73 (2017). Klauda, J. B. et al. Update of the CHARMM All-Atom Additive Force Field for Lipids: Validation on Six Lipid Types. The Journal of Physical Chemistry B 114 , 7830-7843 (2010). Brooks, B. R. et al. CHARMM: The biomolecular simulation program. Journal of Computational Chemistry 30 , 1545-1614 (2009). Darden, T., York, D. & Pedersen, L. Particle mesh Ewald: An N⋅log(N) method for Ewald sums in large systems. The Journal of Chemical Physics 98 , 10089-10092 (1993). Hess, B., Bekker, H., Berendsen, H. J. C. & Fraaije, J. G. E. M. LINCS: A linear constraint solver for molecular simulations. Journal of Computational Chemistry 18 , 1463-1472 (1997). Kühne, T. D. et al. CP2K: An electronic structure and molecular dynamics software package - Quickstep: Efficient and accurate electronic structure calculations. The Journal of Chemical Physics 152 (2020). Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized Gradient Approximation Made Simple. Physical Review Letters 77 , 3865-3868 (1996). Nosé, S. A unified formulation of the constant temperature molecular dynamics methods. The Journal of Chemical Physics 81 , 511-519 (1984). Martyna, G. J., Klein, M. L. & Tuckerman, M. Nosé–Hoover chains: The canonical ensemble via continuous dynamics. The Journal of Chemical Physics 97 , 2635-2643 (1992). Hoover, W. G. Canonical dynamics: Equilibrium phase-space distributions. Physical Review A 31 , 1695-1697 (1985). Ramasubramani, V. et al. freud: A software suite for high throughput analysis of particle simulation data. Computer Physics Communications 254 , 107275 (2020). Additional Declarations There is NO Competing Interest. Supplementary Files SupplementaryInformation.docx Cite Share Download PDF Status: Published Journal Publication published 08 Nov, 2024 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4046811","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":281834778,"identity":"824d1805-3828-4afc-9582-ba16470cd853","order_by":0,"name":"Ritesh Haldar","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAABAElEQVRIie3Qv0sDMRTA8Rce5JZcuz7pgf+CkuEqtPRfSTmwSzd3CQjPpeJq6Z/h4niS1T+hi8tNDidd7uAGU4tSsKmODvlCpuSTXwCx2H8M/RC2hB4YgBqoD7SbUGGCOyI9EQ+GTuyvBPYIKgPfJFh+239+bZ/WpzIpqs24GVK+srKuO8jyAMkcok5fqnNWlV7NDVG2LnG5ZFAX9jAhRDkQ7AST0ejJNZFBTC2oszJIkrZlN2GabXDoT/kkXXeUSEjZTZnmGuGL+N84RvTAk4LV25VYXG7J9EbcMYWJ/7B3f7HxfTJ7hGbkn0KFg6YbTULkUMJu9/r7+lgsFov96APoy00J4iMAFgAAAABJRU5ErkJggg==","orcid":"https://orcid.org/0000-0001-9697-9169","institution":"TIFR Hyderabad","correspondingAuthor":true,"prefix":"","firstName":"Ritesh","middleName":"","lastName":"Haldar","suffix":""},{"id":281834779,"identity":"415774ff-3979-4a5d-80b5-66afdc2cc2ff","order_by":1,"name":"Tanmoy Maity","email":"","orcid":"https://orcid.org/0000-0003-1901-1060","institution":"TIFR Hyderabad","correspondingAuthor":false,"prefix":"","firstName":"Tanmoy","middleName":"","lastName":"Maity","suffix":""},{"id":281834780,"identity":"b7565151-40e8-46f6-b949-49472435a3d5","order_by":2,"name":"Susmita Sarkar","email":"","orcid":"","institution":"Tata Institute of Fundamental Research Hyderabad","correspondingAuthor":false,"prefix":"","firstName":"Susmita","middleName":"","lastName":"Sarkar","suffix":""},{"id":281834781,"identity":"5aaeb5fc-9219-4b59-86e8-1df29d8cc688","order_by":3,"name":"Susmita Kundu","email":"","orcid":"","institution":"TIFR Hyderabad","correspondingAuthor":false,"prefix":"","firstName":"Susmita","middleName":"","lastName":"Kundu","suffix":""},{"id":281834782,"identity":"e5112415-ac6a-4524-a05b-d566aeb1c852","order_by":4,"name":"Suvendu Panda","email":"","orcid":"","institution":"TIFR Hyderabad","correspondingAuthor":false,"prefix":"","firstName":"Suvendu","middleName":"","lastName":"Panda","suffix":""},{"id":281834783,"identity":"f48ec551-16a5-4cea-b5bd-d6b884c5b81e","order_by":5,"name":"Arighna Sarkar","email":"","orcid":"","institution":"Tata Institute of Fundamental Research Hyderabad","correspondingAuthor":false,"prefix":"","firstName":"Arighna","middleName":"","lastName":"Sarkar","suffix":""},{"id":281834784,"identity":"bf10b123-3ef5-4067-9345-5db465249471","order_by":6,"name":"Kalyaneswar Mandal","email":"","orcid":"","institution":"Tata Institute of Fundamental Research Hyderabad","correspondingAuthor":false,"prefix":"","firstName":"Kalyaneswar","middleName":"","lastName":"Mandal","suffix":""},{"id":281834785,"identity":"f0fe97ca-39e1-482a-8b56-31c4142670b7","order_by":7,"name":"Soumya Ghosh","email":"","orcid":"","institution":"Tata Institute of Fundamental Research Hyderabad","correspondingAuthor":false,"prefix":"","firstName":"Soumya","middleName":"","lastName":"Ghosh","suffix":""},{"id":281834786,"identity":"33294a7c-9304-4c38-ae03-ad31130e943a","order_by":8,"name":"Jagannath Mondal","email":"","orcid":"","institution":"Tata Institute of Fundamental Research Hyderabad","correspondingAuthor":false,"prefix":"","firstName":"Jagannath","middleName":"","lastName":"Mondal","suffix":""}],"badges":[],"createdAt":"2024-03-08 16:25:17","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4046811/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4046811/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-024-53207-3","type":"published","date":"2024-11-08T05:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":53160960,"identity":"a61b5d75-9418-4eb4-b1bb-77f12dbb927d","added_by":"auto","created_at":"2024-03-21 10:58:48","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":321675,"visible":true,"origin":"","legend":"\u003cp\u003eA schematic illustration of the dynamic chemical functionalities in oriented nanoporous metal-organic framework thin film; introduction of dynamic chemical interaction between the chemical isomers (shown as green and orange spheres) and MOF reverses the diffusion selectivity; cube = metal-oxo node, hexagonal blocks and cylinders = linkers and pillars in the MOF structure. Diffusion is along the concentration gradient, i.e. along [001] in the studied MOF structure.\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-4046811/v1/ab6aace35f63e4ac161ce889.png"},{"id":53160962,"identity":"52a0b24f-7c79-486b-9c52-9897531962a1","added_by":"auto","created_at":"2024-03-21 10:58:48","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":481480,"visible":true,"origin":"","legend":"\u003cp\u003ea) Surface grown oriented structure of Cu(bdc)(azbpy), optimized at 0 K, b) simulated (black), out (red) and in-plane (blue) XRD patterns of the Cu(bdc)(azbpy), c) 1BP and 2BP vapor uptake profiles at 298 K; black line is the fitting; inset: SEM image of \u0026nbsp;Cu(bdc)(azbpy) thin film (scale = 10 μm).\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-4046811/v1/e7ade0bc0b63a7f2431a29b6.png"},{"id":53160963,"identity":"8324442f-15fd-4d20-97cc-e50ae376856f","added_by":"auto","created_at":"2024-03-21 10:58:48","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":309425,"visible":true,"origin":"","legend":"\u003cp\u003ea) Overview of the 1BP vs 2BP selectivities observed for rigid, flexible and \u003cem\u003ein silico\u003c/em\u003e designed MOFs along [001] direction, using MSD from MD simulations, the scale bars are relative, trend of the selectivity showing the effect of flexibility and chemical functionality; b) a snapshot of the MD simulation during the intrapore passage of the 2BP molecule in the flexible Cu(bdc)(Azbpy), green sphere indicates Br of 2BP; c) the probability distribution for Br···C (of bdc) distance for 1BP and 2BP obtained from AIMD simulation; inset: a snapshot of the AIMD simulation during the intrapore passage of the 2BP molecule in the flexible Cu(bdc)(Azbpy), pink sphere indicates center of mass of 2BP.\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-4046811/v1/706d9f9e447efe65492d7e14.png"},{"id":53160961,"identity":"8d674780-1a01-43f3-93ab-6d8f69ea2aa6","added_by":"auto","created_at":"2024-03-21 10:58:48","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":635993,"visible":true,"origin":"","legend":"\u003cp\u003ea) A schematic of oriented mixed-linker MOF; b) out-of-plane XRD patterns of the Cu(bdc)(azbpy) and Cu(Br\u003csub\u003e2\u003c/sub\u003e-bdc)\u003csub\u003ex\u003c/sub\u003e(bdc)\u003csub\u003e1-x\u003c/sub\u003e(azbpy), x = 0 (black), 0.012 (red), 0.026 (blue) and 0.058 (green); c) left to right: SEM morphology, Br and Cu elemental mapping of Cu(Br\u003csub\u003e2\u003c/sub\u003e-bdc)\u003csub\u003e0.058\u003c/sub\u003e(bdc)\u003csub\u003e0.942\u003c/sub\u003e(azbpy) thin film; d) \u003cem\u003eD\u003c/em\u003e for 1 and 2BP with varying % of Br\u003csub\u003e2\u003c/sub\u003e-bdc; e) adsorbed molecules/pore for 1 and 2BP with varying % of Br\u003csub\u003e2\u003c/sub\u003e-bdc, the shaded regions indicate a crystalline phase, different than parent structure Cu(bdc)(azbpy).\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-4046811/v1/defd875be65e9c37a947a64b.png"},{"id":68606130,"identity":"d02d3003-a0aa-4607-8f2b-096654c69a4f","added_by":"auto","created_at":"2024-11-09 08:07:16","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2313583,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4046811/v1/db43815d-ea43-4cd2-871c-96f1f4adf122.pdf"},{"id":53160965,"identity":"f321e4ae-f2db-4d11-b2d7-b524301ec242","added_by":"auto","created_at":"2024-03-21 10:58:49","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":7825128,"visible":true,"origin":"","legend":"","description":"","filename":"SupplementaryInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-4046811/v1/7659b568f5af282eae957dcf.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Steering diffusion selectivity of chemical isomers within aligned nanochannels of metal-organic framework thin film","fulltext":[{"header":"Introduction","content":"\u003cp\u003eNanoporous materials such as zeolites,\u003csup\u003e1\u003c/sup\u003e metal-organic frameworks (MOFs)\u003csup\u003e2,3\u003c/sup\u003e and covalent-organic frameworks (COFs)\u003csup\u003e4\u003c/sup\u003e hold substantial importance in applications involving chemical storage, separation and catalytic conversions. The significance of these nanoporous materials has grown significantly;\u003csup\u003e5,6\u003c/sup\u003e especially since they offer sustainable, energy economic and low carbon footprint technologies, e.g membrane based chemical separation.\u003csup\u003e7-9\u003c/sup\u003e In these practical contexts, the prevalent factor influencing efficiency is molecular diffusion.\u003csup\u003e8,10-12\u003c/sup\u003e The movement of the molecules through chemically functionalized channels of the nanoporous materials is influenced by various factors, including chemical interactions (adsorbate-adsorbent), concentration gradient, channel size and shape.\u003csup\u003e12\u003c/sup\u003e Occasionally, using imaging\u003csup\u003e13\u003c/sup\u003e and spectroscopic techniques\u003csup\u003e14\u003c/sup\u003e it has been possible to visualize the molecular diffusion path.\u003csup\u003e12\u003c/sup\u003e However, modulation of diffusion and subsequent manipulation of material properties pose significantly greater challenges.\u003c/p\u003e\n\u003cp\u003eAmong the nanoporous materials, MOFs are crystalline, versatile topology, high porosity (surface area \u0026gt; 7000 m\u003csup\u003e2\u003c/sup\u003e/g) material and well-known for chemical storage, separation,\u003csup\u003e15,16\u003c/sup\u003e sensing\u003csup\u003e17\u003c/sup\u003e and catalysis\u003csup\u003e18,19\u003c/sup\u003e applications. A great number of literatures reflect applicability of MOFs as functional nanoporous material, and also the successful chemical design strategies that have improved their performance. Notably, while many of the synthesized MOFs excel in adsorption-based separation (i.e. at equilibrium),\u003csup\u003e15\u003c/sup\u003e relatively a few serve as membranes (~1 % of the all known MOFs),\u003csup\u003e9,20\u003c/sup\u003e relying on differences in diffusivity for separation. The reason of relatively fewer selected MOFs for membrane based separation is (apart from processibility issues) that a predictive design of pore geometry and functionality for diffusion control is far more challenging than the adsorption process.\u003csup\u003e21,22\u003c/sup\u003e For the heterogeneous catalysis too, role of substrate diffusivity is not well investigated. One mechanism of overcoming this challenge is to develop a computational screening approach. By simulating molecular diffusion within MOF pores, not only may the sampling volume can be accelerated, but it can also offer insights into the interactions between the adsorbate and MOF (thermodynamic and kinetic).\u003csup\u003e23-25\u003c/sup\u003e Utilizing knowledge of diffusivity and interactions, it becomes feasible to tailor porous materials to exhibit targeted molecular diffusion, facilitating chemical separation and catalysis. While the computational screening approaches for MOF-membrane design have received a significant interest,\u003csup\u003e26,27\u003c/sup\u003e experimental manipulation of diffusivity has remained challenging. Recent experimental efforts, such as downsizing MOF crystallite size, morphology control,\u003csup\u003e28\u003c/sup\u003e controlling nanochannel orientation\u003csup\u003e29-31\u003c/sup\u003e and employing novel heterostructure design\u003csup\u003e32-36\u003c/sup\u003e improve molecular diffusivity, however do not predictively tune the diffusivity.\u003c/p\u003e\n\u003cp\u003eIt is evident that for controlling molecular diffusion, a comprehensive strategy to assess the thermodynamics and kinetics is much needed. In this communication, we have employed a strategy incorporating both precise measurement of mass uptake kinetics and molecular dynamic (MD) simulation. This approach was applied within a specifically designed and functionalized nanochannel of (pillared-layer) MOF thin film to understand and regulate molecular diffusion of chemical isomers. Our findings confirm that nanochannel orientation, distribution of chemical functionality on the pore surface and framework dynamics work in tandem to regulate molecular diffusion rate and direction. Leveraging these insights, we establish an adsorbate-MOF \u0026ldquo;dynamic chemical interaction\u0026rdquo;. The unveiled dynamic interactions profoundly influence molecular diffusion; as we evidence, certain linker-adsorbate interactions can enhance or hinder diffusion on the basis of framework dynamics. In the following discussion, we have illustrated a chemical strategy to implement the \u0026ldquo;dynamic chemical interaction\u0026rdquo; and utilizing this we have achieved an unprecedented reversal of diffusion selectivity for 1 and 2-bromopropane (1BP and 2BP) positional isomers in the nanoporous MOF thin film (Figure 1).\u003c/p\u003e"},{"header":"Results ","content":"\u003cp\u003eThe various factors governing molecular diffusion in MOFs include: i) pore window and cavity size, ii) orientation of nanochannels, iii) distribution of chemical functionality on the pore surface, iv) adsorption enthalpy and v) linker/framework flexibility.\u003csup\u003e12\u003c/sup\u003e Although these factors are well recognized, combined effect of these are challenging to perceive and implement. We have considered each of these factors to design a MOF thin film and study the diffusion selectivity of 1BP and 2BP isomers. The halogenated alkane isomers are commercially important chemical feedstocks (for lubricants, pesticides, PVC production)\u003csup\u003e37\u003c/sup\u003e and very few studies highlighted the possibility of adsorptive separation of these isomers.\u003csup\u003e38\u003c/sup\u003e We chose the brominated isomers as a proof of concept to demonstrate the potential of “dynamic chemical interaction”. Firstly, we outline the design strategy of the oriented nanochannel MOF structure and evaluate the diffusion selectivity for the isomers. Subsequently, we establish the dynamic chemical interactions in the MOF thin film and apply those to reverse isomer diffusion selectivity.\u003c/p\u003e\n\u003cp\u003eThe selected nanoporous system is a pillared-layer type MOF\u003csup\u003e39\u003c/sup\u003e (Figure 2a); a Cu\u003csup\u003e2+\u003c/sup\u003e-dimeric paddle-wheel node is linked by bdc (1,4-benzenedicarboxylic acid) to form a square-grid type 2D layer. This 2D layer is pillared (along [001] axis) by a azbpy (4,4'-azobipyridyl) to form a PCU topology Cu(bdc)(azbpy) MOF having two distinct pore windows. The window dimensions are 7.3 Å × 4.3 Å (along [001]) and 9.7 Å × 6.9 Å, calculated by adding van der Waals surface in a periodic density functional theory (DFT) optimized structure (at 0 K). To realize the MOF pore window orientation, as illustrated in Figure 2a, we have used a layer-by-layer, liquid-phase epitaxial growth technique.\u003csup\u003e40,41\u003c/sup\u003e A self-assembled monolayer (-OH terminated) functionalized Au surface was alternately exposed to Cu(CH\u003csub\u003e3\u003c/sub\u003eCOO)\u003csub\u003e2\u003c/sub\u003e and mixture of bdc and azbpy linkers solution to grow the surface anchored MOF or SURMOF (described elsewhere).\u003csup\u003e39\u003c/sup\u003e Out-of-plane x-ray diffraction (XRD) pattern exhibited diffraction peaks related to (001) plane, and in-plane pattern exhibited diffraction peaks related to (100) and (010) planes (Figure 2b). This confirmed a [001] oriented SURMOF, as illustrated in Figure 2a. The scanning electron microscopy images confirmed a monolithic film growth, as illustrated in Figure 2c. Note that the pore window dimensions are large enough to allow diffusion of the bromopropane isomers (1BP = 8 Å × 4.7 Å; 2BP = 6.9 Å × 6.6 Å, calculated by adding van der Waals surface). For the [001] oriented SURMOF, the Cu(bdc) planes are exposed to the surface. Hence, we anticipated that the geometry based adsorption and diffusion selectivity for the bromopropane isomers will be regulated by the 7.3 Å × 4.3 Å sized pore window.\u003c/p\u003e\n\u003cp\u003eTo measure the adsorption and diffusion selectivities, we have used quartz crystal microbalance (QCM) technique.\u003csup\u003e39,42\u003c/sup\u003e In this method, SURMOF is grown on Au-coated quartz crystal sensor and mounted inside a fluidic cell. A constant flow of saturated solvent vapor through the fluidic cell allow measuring the mass uptake (mass is calculated using Sauerbrey equation, see experimental section). For the Cu(bdc)(azbpy) thin film, the mass uptake profiles for the isomers are shown in Figure 2c and Figure S1. We describe the uptake profiles using an exponential decay function\u003csup\u003e43\u003c/sup\u003e:\u003c/p\u003e\n\u003cp\u003e\u003cimg src=\"data:image/png;base64,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\"\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003eOne possible explanation of this opposing trend of adsorption and diffusion is following: higher adsorption is due to stronger adsorbate-adsorbent interaction, which reduces the molecular mobility.\u003csup\u003e51\u003c/sup\u003e To appraise this observation, MD simulation was performed on the most probable conformation obtained from AIMD simulation of the periodic unit of Cu(bdc)(azbpy) at 300 K (see supporting information). At first we have excluded framework dynamics, because we anticipated only adsorbent-adsorbate interaction-driven diffusivity trends. As illustrated in Figure 3a and S2, the diffusion selectivity along [001] axis was found to be 1BP\u0026gt;2BP (estimated from mean square displacement, MSD, See Table S1). This is in contrary to the experimental observation and also implies that only adsorbate-adsorbent interaction strength is not the governing factor. In the next step, we have introduced framework dynamics and performed a similar simulation as done for rigid framework. Comparison of the MSD profiles indicated a selectivity trend of 2BP\u0026gt;1BP, in accordance to the experimental data. Assessment of the effective close proximity interactions (g(r)) between isomers and host framework revealed that the most influential chemical group in the framework is the bdc (Figure S3). The faster diffusion of 2BP in comparison to 1BP can be rationalized based on following order of interactions: 2BP – bdc \u0026gt; 1BP – bdc, 1BP – azbpy \u0026gt; 2BP – azbpy. Analysis of the specific Br – MOF interactions reveals that there is a stronger specific Br – bdc i.e. Br– π interaction for 2BP than 1BP (Figure 3b and S4). The specific Br – π(bdc) interaction is further validated by performing ab initio MD (AIMD) simulation and analyzing the trajectory during the timespan of intrapore molecular movement (see experimental section, Figure 3c; note that the diffusion selectivity observed in this simulation is same as the one observed in MD of flexible MOF, see Figure S5a). Stronger interaction with bdc accelerates diffusion, while stronger interaction with the azbpy decelerates diffusion. These observations underscore that in addition to the chemical interactions, the framework dynamics also contribute to the overall driving force. We term this effect as “dynamic chemical interaction”, a phenomenon validated in subsequent sections.\u003c/p\u003e\n\u003cp\u003eDrawing from the MD simulation insights, we have \u003cem\u003ein silico\u003c/em\u003e reconfigured the pore windows along [001] orientation; i.e. substituting the bdc linker with a Br\u003csub\u003e2\u003c/sub\u003e-bdc (2,5-dibromobenzene-1,4-dicarboxylic acid) linker. This intuitive chemical functionality transformation changes not only the specific chemical interactions between the chemical isomer and the bdc linkers but also changes the framework dynamics.\u0026nbsp;The change in the framework dynamics of the bdc linkers is also captured in the most probable configuration obtained during AIMD simulation of the\u0026nbsp;Cu(bdc)(azbpy) and Cu(Br\u003csub\u003e2\u003c/sub\u003e-bdc)(azbpy) at 300 K (Figure S5). We have performed a similar set of MD simulation for Cu(Br\u003csub\u003e2\u003c/sub\u003e-bdc)(azbpy), as done for Cu(bdc)(azbpy) (\u003cem\u003evide supra\u003c/em\u003e). As evident from the Figure 3a and S6, the MSD values obtained appear very different, than those observed for Cu(bdc)(azbpy). Mainly, 1BP diffusion is found to be relatively faster. Inspection of the close proximity interactions revealed following order: 1BP – Br\u003csub\u003e2\u003c/sub\u003e-bdc \u0026gt; 2BP – Br\u003csub\u003e2\u003c/sub\u003e-bdc and 1BP – azbpy \u0026lt; 2BP – azbpy (Figure S7-8). This reverse order of interactions reverses the diffusion selectivity. We attribute this reversal to the proposed dynamic chemical interaction, as the diffusion is effected by chemical interaction and framework dynamics.\u003c/p\u003e\n\u003cp\u003eNext, we have experimentally attempted to execute the \u003cem\u003ein silico\u003c/em\u003e findings. Attempts to synthesize an isostructural, oriented Cu(Br\u003csub\u003e2\u003c/sub\u003e-bdc)(azbpy) thin film akin to Cu(bdc)(azbpy) proved unsuccessful (Figure S9). However, a successful strategy emerged through a mixed-linker approach,\u003csup\u003e21,52-55\u003c/sup\u003e yielding Cu(Br\u003csub\u003e2\u003c/sub\u003e-bdc)\u003csub\u003ex\u003c/sub\u003e(bdc)\u003csub\u003e1-x\u003c/sub\u003e(azbpy) (x = 0.012, 0.026 and 0.058) thin films (x was quantified by (reverse phase HPLC, see Figure S10). These mixed-linker MOF thin films maintained high crystallinity, preferred [001] orientation and exhibited homogenous surface coverage, as evidenced by the out-of-plane XRD, SEM images and elemental analysis and mapping ((Figure 4a-c, S11-14). Subsequently, we conducted 1BP and 2BP vapor uptake experiments using QCM for these mixed-linker MOF thin films (Figure S15). Similar to the case of Cu(bdc)(azbpy), we have calculated the saturation adsorption amount/pore and \u003cem\u003eD\u003c/em\u003e. The Br\u003csub\u003e2\u003c/sub\u003e-bdc % vs \u003cem\u003eD\u003c/em\u003e and adsorption amount/pore plots are presented in Figure 4d-e. Across all the mixed-linker thin films, the saturation adsorption amounts are higher for 1BP, resembling the trend observed in the parent structure Cu(bdc)(azbpy). Moreover, with increasing % of the Br\u003csub\u003e2\u003c/sub\u003e-bdc, adsorption amount decreased for both the isomers. This reduction in adsorption can be attributed to the steric effect introduced by the bulky –Br atoms. Surprisingly, a reversal in \u003cem\u003eD\u003c/em\u003e is observed for Cu(Br\u003csub\u003e2\u003c/sub\u003e-bdc)\u003csub\u003e0.058\u003c/sub\u003e(bdc)\u003csub\u003e0.942\u003c/sub\u003e(azbpy) thin film. In comparison to the parent structure, \u003cem\u003eD\u003c/em\u003e value for 2BP decreased \u003cem\u003eca.\u003c/em\u003e 8x and for 1BP increased \u003cem\u003eca\u003c/em\u003e. 0.5x.\u003c/p\u003e\n\u003cp\u003eThe experimental observation may be correlated to the \u003cem\u003ein silico\u003c/em\u003e experiment; however several other factors merit consideration: i) inhomogeneous mixing of the linkers leading to segregated crystalline phases, ii) the presence of structural defects, and iii) changes in crystalline domain sizes. These three factors are discounted based on the following experimental observations: a) Out-of-plane XRD patterns of the mixed-linker thin films did not reveal new diffraction peaks, confirming that a new crystalline phase of Cu + (Br\u003csub\u003e2\u003c/sub\u003e-bdc) +(azbpy) did not form. However, when the Br\u003csub\u003e2\u003c/sub\u003e-bdc % increased to 17, new diffraction peaks emerged (Figure S16). This confirmed that mixed-linker phase is feasible only for low % of Br\u003csub\u003e2\u003c/sub\u003e-bdc. b) IRRA spectra of the mixed-linker and parent Cu(bdc)(azbpy) confirmed that the asymmetric and symmetric –COO stretching vibrations of the paddle-wheel node (1630 and 1388 cm\u003csup\u003e-1\u003c/sup\u003e, respectively) remained unaltered (Figure S17). This underscores the absence of new crystalline phase. In the case of 17% Br\u003csub\u003e2\u003c/sub\u003e-bdc, the asymmetric and symmetric –COO stretching vibrations are different than those of the mixed-linker MOFs, consistent with the out-of-plane XRD patterns (Figure S17). c) Comparison of the (001) diffraction peak full width at half maxima for the mixed-linker and parent structure confirmed very similar crystalline domain sizes (30-34 nm) (Figure S18). d) SEM images and elemental mapping of the mixed-linker film confirmed the homogenous coverage and uniform distribution of the Br\u003csub\u003e2\u003c/sub\u003e-bdc functionality (Figure 4c). Based on these observations, the reversed selectivity can be attributed to the chemical interactions which are observed for the \u003cem\u003ein silico\u003c/em\u003e designed Cu(Br\u003csub\u003e2\u003c/sub\u003e-bdc)(azbpy). Note that a higher concentration of Br\u003csub\u003e2\u003c/sub\u003e-bdc in the Cu(bdc)(azbpy) may have more prominent effect on the diffusivity (i.e. selectivity); however those structures could not be realized experimentally.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThe chosen pillared-layer type MOF thin film exhibits distinct pore windows and functionality along the concentration gradient (i.e. [001]). Using these oriented nanochannels, we have concluded that diffusivity of two chemical isomers (1BP and 2BP) can be precisely manipulated and reversed using chemical design principles. To arrive at this conclusion, we have compared the observed chemical isomer diffusivities within a pillared-layer MOF thin film with those obtained from MD simulation. It is evident that diffusion has an intriguing dependence on the framework dynamics, while specific chemical interactions (like Br-\u0026pi; interaction) are also substantially important. We have hypothesized that the framework dynamics and chemical interactions as tool to predictively alter the chemical isomer diffusivity. Initially \u003cem\u003ein silico\u003c/em\u003e and later by using a mixed-linker approach we have shown that diffusivity of isomers can be reversed. To ensure that the experimental findings are exclusively attributed to the dynamic chemical interaction, we have performed careful characterizations of the thin films. The experimental observations and the hypothesized chemical strategy are unprecedented. Although this predictive alteration of diffusion is currently showcased for a pair of haloalkane isomer within pillared-layer type MOF, it\u0026rsquo;s important to note that the chemical design route transcends the boundaries of specific isomers and porous materials. In the future, the proposed methodology will be implemented to improve separation efficiency of the chemical isomers which are more challenging to perform using conventional distillation technique.\u003c/p\u003e"},{"header":"Material","content":"\u003cp\u003eCu(CH\u003csub\u003e3\u003c/sub\u003eCOO)\u003csub\u003e2\u003c/sub\u003e\u0026middot;H\u003csub\u003e2\u003c/sub\u003eO, 1,4-benzenedicarboxylic acid (bdc), 2,5-dibromobenzene-1,4-dicarboxylic acid (Br\u003csub\u003e2\u003c/sub\u003e-bdc), anhydrous n-bromopropane (1BP) and iso-bromopropane (2BP) were purchased from Sigma-Aldrich. All chemicals were used as received without further purification. QCM Sensors (5MHz) were purchased from openQCM.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMethods:\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis of 4,4\u0026apos;-Azobipyridine\u003c/strong\u003e: 4,4\u0026apos;-azobipyridine was synthesized following a reported method.\u003csup\u003e56\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis of pillared-layer MOF thin films on QCM sensor\u003c/strong\u003e: 5 MHz (Au coated) QCM-sensors were dipped in an ethanolic solution (20 mM) of 11-mercapto-1-undecanol (MUD) for 24 hours to obtain \u0026ndash;OH functionalized surface. These substrates were then thoroughly washed with absolute ethanol (99.99%), dried and used for thin films synthesis. The MOF thin films were prepared on those functionalized substrate \u003cem\u003evia\u003c/em\u003e a well-known layer-by-layer (lbl) liquid-phase epitaxial (LPE) method.\u003csup\u003e57\u003c/sup\u003e The method consists of four steps to complete a cycle at 60 \u0026ordm;C as: i) dipped in 1 mM copper acetate ethanol solution for 15 minutes, ii) drained the metal solution and washed with fresh ethanol, iii) dipped in 0.2 mM linker solution (mixture of two linkers) in ethanol for 30 minutes and iv) drained the linker solution and washed with fresh ethanol. MOF thin films with varying doping percentage were prepared by varying the linker solution in different Br\u003csub\u003e2\u003c/sub\u003eBDC proportions. 4,4\u0026apos;-azobipyridine is the only pillar linker used with either 1,4-Benzene dicarboxylic acid linker or mixture of two dicarboxylic acids (1,4-Benzene dicarboxylic acid and 2,5-dibromobenzene-1,4-dicarboxylic acid) for MOF thin films upto 60 cycles.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCharacterizations\u003c/strong\u003e:\u0026nbsp;\u003c/p\u003e\n\u003cp\u003ePowder x-ray diffractometer (XRD) patterns of thin films were recorded on a Rigaku XDS 2000 diffractometer using nickel-filtered Cu K\u003cem\u003e\u0026alpha;\u003c/em\u003e radiation (\u003cem\u003e\u0026lambda;\u003c/em\u003e= 1.5418 \u0026Aring;) ranging from 5 to 20 \u0026deg; at room temperature (voltage 40 kV, current 200 mA). Out-of plane PXRD was recorded in 2\u003cem\u003e\u0026theta;\u003c/em\u003e/\u003cem\u003e\u0026theta;\u003c/em\u003e (step size 0.01, scan rate 0.2 \u0026ordm;/s), in-plane in 2\u003cem\u003e\u0026theta;\u003c/em\u003e/\u003cem\u003e\u0026phi;\u003c/em\u003e geometry with grazing incident angle (\u003cem\u003e\u0026omega;\u003c/em\u003e) at 0.5 \u0026ordm; and step size of 0.12 with scan rate 0.1 \u0026ordm;/s.\u003c/p\u003e\n\u003cp\u003eSurface morphology of the MOF thin films were characterized using field emission scanning electron microscopy (FESEM), JEOL JSM-7200F instrument with a cold emission gun operating at 5 kV. Energy-Dispersive X-ray spectroscopy (EDS) elemental analysis and mapping were also done on the FESEM (at 15 kV).\u003c/p\u003e\n\u003cp\u003eIRRA (Infrared Reflection Absorption) spectrum (4000\u0026ndash;600 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e) was collected under vacuum using Bruker VERTEX 70v with 2 cm\u003csup\u003e-1\u003c/sup\u003e resolution and with 128 scan rate.\u003c/p\u003e\n\u003cp\u003eX-ray photoelectron spectroscopy (PHI versaProbe III) was performed for the MOF thin films under ultrahigh vacuum (10\u003csup\u003e-9\u003c/sup\u003e bar) environment.\u003c/p\u003e\n\u003cp\u003eThe adsorption (mass uptake) profiles were measured using a quartz crystal microbalance (QCM) from open QCM, Italy.\u003c/p\u003e\n\u003cp\u003eThickness for all the thin films was calculated using J.A. Wollam ellipsometer (alpha-SE). The data was fitted using a B-Spline model including surface roughness.\u003c/p\u003e\n\u003cp\u003eAnalytical reverse-phase (RP) HPLC was performed on an Agilent HPLC instrument using an Agilent zorbax SB-C3 (5 \u0026mu;m), 4.6\u0026times;150 mm reverse-phase column at a flow rate of 0.9 mL/min using a linear gradient of solvent B in solvent A at 40 \u0026deg;C (solvent A = 0.1% TFA in H\u003csub\u003e2\u003c/sub\u003eO; solvent B = 0.08% TFA in acetonitrile). The 214 nm UV absorbance of the column eluent was monitored. During sample preparation, compounds were weighed out in their mentioned ratios and dissolved in 200\u0026micro;L of DMSO. From this stock solution, 5\u0026micro;L was taken and diluted with 60\u0026micro;L DMSO and 60\u0026micro;L of B solvent (B = 0.08% TFA in acetonitrile). Then 0.5 \u0026micro;L injected in HPLC for analysis.\u003c/p\u003e\n\u003cp\u003eMOF thin films deposited on QCM substrate were dipped in 18 mM aqueous solution of Na\u003csub\u003e2\u003c/sub\u003eEDTA\u0026middot;2H\u003csub\u003e2\u003c/sub\u003eO (Na\u003csub\u003e2\u003c/sub\u003eEDTA = ethylenediaminetetraacetic acid disodium salt) to disintegrate the MOF structure and remove Cu\u003csup\u003e2+\u003c/sup\u003e from the solution. After pH adjustment to ~6, the clear aqueous solution (obtained by centrifugation) was taken for the (RP) HPLC analysis.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eQCM experiments\u003c/strong\u003e: MOF thin films were activated at 65 \u0026deg;C at 0.1 mbar. Mass uptake experiments were carried out using a constant flow rate (50 sccm) of dry N\u003csub\u003e2\u003c/sub\u003e, passing through saturated solvent vapors (1 and 2BP).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAnalyses of uptake kinetics\u003c/strong\u003e: Mass-frequency relationship for the QCM measurements is given by Sauerbrey equation;\u003csup\u003e42\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003e\u003cimg src=\"data:image/png;base64,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\" width=\"213\" height=\"53\"\u003e\u003c/p\u003e\n\u003cp\u003eWhere n denotes the overtone order (n = 3, 5, and 7) and c is the mass sensitivity constant. For a 5 MHz crystal, c has value of 17.7 ng/cm\u003csup\u003e2\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eWe examine the data with the assumption of Fickian diffusion, that is, we assume a constant diffusivity, \u003cem\u003eD\u003c/em\u003e, is independent of the vapor concentration.\u003c/p\u003e\n\u003cp\u003e\u003cimg src=\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAdoAAABCCAYAAADwphc1AAAPCElEQVR4Ae2ai5HUOhBFNwViIAVyIARiIAUyIAMyIAIiIAESIANymFdnX93appFkaWx57PFV1ZRtfVrSUauv7N2Xm5MJmIAJmIAJmMA0Ai/TLNuwCZiACZiACZjAzUJrJzABEzABEzCBiQQstBPh2rQJmIAJmIAJWGjtAyZgAiZgAiYwkYCFdiJcmzYBEzABEzABC619wARMwARMwAQmErDQToRr0yZgAiZgAiZgobUPmIAJmIAJmMBEAhbaiXBt2gRMwARMwAQstPYBEzABEzABE5hIwEI7Ea5Nm4AJmIAJmICF1j5gAiZgAiZgAhMJWGgnwrVpEzABEzABE7DQ2gdMwARMwARMYCIBC+1EuDZtAiZgAiZgAhZa+4AJmIAJmIAJTCRgoZ0I16ZNwARMwARMwEJrHzABEzABEzCBiQQstBPh2rQJmIAJmIAJWGjtAyZgAoch8Pv379unT59uLy8vr7+vX78eZmxbDeQKc9yK1bPYsdA+y0p6HibwBAR+/vx5+/Dhw+3Pnz+3Hz9+3D5+/Ng9K+p//vz5tW13o8kVS2NaM8fJw7X5SQQstJPA2qwJXI2A3kJ1fffu3avw8QZ3T/r27dvt+/fvXU2ph8geMf369ev1wMDhIaeROea2fj4PgSlCy4lNm437mPRZaOSkGttf8V4bVUyPdmo/w5oQ5L58+TL0hnSGeT1qjIgnQhr3N3n4qPLwW95OqTcqtjUBIm7kz8nYfv/+/V8oEF76ZjyU9Qr2X0YGHxhHaXyYYcx53LU5Dnbr6icgMEVomTcOh6NHB+czCpuOX+l0dwJeDxkigUKndQUVRMOpjwABDX74ow94fcyWasERv5Soqn4UWvLY5+x3+a/qta7EDMWN3I4+s2DxHPcDY6KexJ3DPWNYm7Bb8x/GyRjoJ4+PfhlLHENrjmvH6fbHIzBNaAlqOJ6cTqc9nJ6fUz+BHLzY7GbYz08BF1+sBcp+a67JvkYoEI4loYUWIiTutMOfSz/qsFa5TMQRz1gmm1w5xNcSZbQlMV5s0AZ/YA78qMO8KNNzttcSWvmY7Oa2PGOXt/zWHEvtnHd+AlOEFmdic/EmETcD+Tgb+U79BDi06GTPJiVotAJLv+Vr1bTQrl9vxEaHPESpR2jFHd/Fj7NglezURkpd7MVEjMnjyOVxv+jNU22YD3FJz9jTHKOdPO5YpvuW0C6NUzZ8fT4CU4RWf3vAMREJntkcCC0bRac/cOJ85DvVCcCLQAA7fgQBf3qv86qVKODXyp3fJoDPsZ/le/ii9rhaKk/PXOMbLc9ZsEptYvt4T90RoaVvfYaWnewHrWfK6LP2k01dLbQi4WskMEVocTbEgR8OyjMJwdUnHJ7ZtHJg1YmD8/3/f+OCk4KFgp3ecGuMYC22S9cYuGiHqPNTfvykprxav0fOZ+xX8zMOsRzM5D9r1gd+JV/CP5UoR0iV8Fd8CR9SmiG08Y1V/ZRElrLsB0vPspfHrfx4xb+wV0pwWHqpYK0Ytw4zJTvO6yOAz0VfrLWiTm3Nam1G8zcXWhyEzabEvZwLJ4yBjgnGTao2R7syfsbds2hbj52+YYgAkuDLWEqftnLfOsiobSzHDhsa23Iy+qINZSqnL/I4NJFHv1rPaO8M94z9DP62FUvElYPtrPXCd6LA6WCtfUK/MEdg8B0l2sQ4gB3a0H4psX4Sbc0L/1We2meRjfuFuvJz6utZbfOz8hljHLfydWWO8M5joZy5waEn6bCr+fW0cZ03AqwD66u4Ron2Ar7GGsUyyvGX6BNv1ra5e1PEbey9OmIM3jLLxMjXpiKfvJIIqM2jryyYxCiOe+9xRSdhHIwpBq7aeNio1GeDl4IYNiiX0xFIdI9Nlce2lMc6tb6PlM94mWf8nW0OozxZy9q6j9oq1UcsxVPletaVgIavRv+hLuyjYBHgGGvPWzd1sI9tiTz2edaeYO4aQ7zSdyxjHEvPmpvaxnHHMvJjX9xjW4m+RnyOuBjnJDu+LhPgUBV1BT+BPf7Bj3vWJ68HvspvRtpcaEcGiXPijGyevBlH7Myqy4IxPm3GuHFm9bm1XU7XOFUtQDBHORzCTD05JAGQn4SdfDHZepy2ty0BgrTWdVvLx7RGDJkVJNfOOO6rEVvsvSut4QibWl1iNL4fUxRd5RPnSl8YaDsjzj9UaCUCpU8tAnKE65mFFnHEeRDbksNlvqwFDkh9rQubnTx+ysvt/LxMQG8psGVN9GlQb2nka/NTpnVAQGIdHXhUn7KY9LZ5xMNrHOfW98z7aGKrMbFmo4l1lT+Mtr1qfQS0J84R09g/OZFfeynJdUee/+1ppPWB6koMgdf63XNake172h4BkcbPpr1a8D0Cf8agw4p8SAcaBWAJKfWU2PBROGiDb5PHOtKWe/LiupLH25DTuQmwpqytfObcs5k/+hFe7CW+zuWkWBn3U65zz/PTCO09k+9tI/hndngF5BmntV6OV67HISd+DUAkCaLx9M0a6TDEm1AOBDqFxyAgO1mgvc7P4W34SFzb55jVnFnosNpjvfaJWPspfyXqsdmqc7fQ4gB7/lqTmF02IrQEuF4uJeHubVuq1+KAAxHEabe1E7X67SkrzeXMeXnONf/hrTOLL3n88CPWLCYJbczjnvpRlFnnWnBe459nXpOzjD2vLeOurWWue/Xn2v7IXDjcxn2Xy2cwv1to8+Ae/axgtrShSuK2NHbZvqftku09y+WI+tvgnn1fuS/5T8k385un6pYCgdYvs8RGtDMjUOQ+/bwPgdG1zAcp+UX2PYl3KV8+GMvIq+XLL2N96NTya2Os5Ue73GvseQXUX86Pz8Q+vhy1UquPVrtW2dMIbWuSa8vkYFzPmvRGGz9V7jUXNoDepksCstc4HtXPiP/oLZfNnv2tFkj4DBaDR+uN9lEM3O99BEaD/qhYYT/+8DH5a8wnr5Yvv4z1mW0tvzbGWn60yz12S0n9lcrIIwbSR/5SlOu3+sh1e58ttB2k5GBcz5pwMH57J/7WiBDwd0V+iMAjxH7vecf+2Nhs3qV5I5b6rM+nYFjFoKBAEvNKth+11nHOvt+GwIygv83IjmdFf6ON+0OjJI/9Fct4uy0d/GGufaj2a68W2g6CiMWZHZ4An4N2adoEaAmC7rnikIglZTwrqQ75+ad6CEZ0Zu5VJjtXuLLJWQMd1jh0kKdnRJS3WSUJKKwUHCS0ChgKHnltKWe9nM5NgH3HvpKPnHs280fPnirxgiN7K8conrOgwpp8bG2ZLLQNmohCXiB92ms0m16EcEr49LZY61SblcPCUlJwVyBXWz3LCcnvTQgFAqHE/bMILZuRg4Q2cJyn5qtrFEXq40daE9ZTNrTxYa48/aNTFFqVwTKvhw6GWwcLzeUM15G1Oep8dEA+6viOOK4cb/ADDqLaL/mqQ6zmAnP25tbJQrs10R3s4UwKyDhF68RLOUG7lvIbJo4Y7S091+wqPzv+ktDi+IxJ85OdR18ZdxZSOMGXMSNuzHVmktD29MEBLI+3p91Z64iN1mDvtZnB7WpruAVD1h1u9yba6gB8r41Su1VCy6R0QuA+Jp305fixzPfbECDAwzmfymQdwcJxauU67cWAvCSssZy11frnq9adaxR6xqQ3NI1TV8ZJ/fiGhuAiZthnLnsIsDZr9mn6jnPRuLlyEp49NolJ7Ld2z9g5yV/prRa/kt9FLnusTexvi3vG3Nq7W/TxrDbYo7V92pozzGuxqdWup2yV0NIBjk0gjEGGEwGbPP/tqGdArtNHgACKM9VElECbxa/2LKHFFnW0lnrWCS8/94wU51XAp31LLJmP+sa2BE9iwSbA1tqE3VJAph/64DAAB+rlRLucv1cg17jEI48tP8OSvRkPLrnOMz3jx3ld91qbLTlqz1xl3bZkhy3iDH4/Irb4Dm1oOyOtFloGRwBQsCYI4OwErFmngxkgjmJTTlITRYI8dSSy8Bb7OAfWoGYj56t9bIOtpefYX+teAoFIcl9LjKvl6Ag+Qk2CA/UZI+PHNj/qxP50SIh90pZ2OdG3+sd2FlTqI17Rr3nW4WBkY+e+l57pQ+s2ctggWDNejXGpnzOX4wdxXfdamy2ZsVba21vavaIt/KG0hzML6hAztPdz+RbPq4SWTYxTcAKTg3Mln2BAvtMYARYcfnCUk+QAAnMFXa6Unz0xVw5trQSTKJywws/EiSAVn6kfRVG2qU9ZK9WEVr5NWw45cR24d3ocgbhPvDaPWwf3/C+BVZFBn2UUJHnG2QlGBB2c/d5EIMTOVRPzl4DEAPKsPJbEj8NFfivLXFrPlGVRjM+ZK2XiXyrLeX5+PIG8/o8fkUdgAv8TWCW0iAFiqtOj3hIQXH3ioxsCJG8aBC/eQpS4J4+y+DbDvYKgbKrNVa4W2reVLokspTmwLj3L4pKoU89CK1rnueb1P8/IPdJnJ3C30PI9m2CkxL3eQBGJKJCILmJMOZuBxJXPetjhc2D8xEcgjMKrPq50Zf56o1IAWfOF4OjsamueRTb6CQc1OOlvK3rWXPOz8peEVl9k4mdqtaWMg6HT8QjgK1ePG8dbFY8IAm9KOcgDIUVcJZxqzjP5/CQUBCzElsCnRLCScJAf/56LjfisNle6Zn48w1yi8owsmGOcH/5DXv4x91iGvyw9R17UjQfBWJb74jkmvs5EsY9lvn8cgbz+jxuJezaBfwn8HUX+LV+dg4jyFkAAjW8CBDDy2CDkI8Z6gyAIkk9QkxivHogNHJ4AbyRHP2DJNw8P0wM0ARM4DIHpQkvw1FtCfKPlrYB83ka4540XQSZRj7JY/zDEPJBpBDh4IWTyg2kd3WmYgx/+7GQCJmACIwSmC+3IYFzXBBBbDlj6unEUIhwI+TmZgAmYwCgBC+0oMdc3ARMwARMwgQECFtoBWK5qAiZgAiZgAqMELLSjxFzfBEzABEzABAYIWGgHYLmqCZiACZiACYwSsNCOEnN9EzABEzABExggYKEdgOWqJmACJmACJjBKwEI7Ssz1TcAETMAETGCAgIV2AJarmoAJmIAJmMAoAQvtKDHXNwETMAETMIEBAhbaAViuagImYAImYAKjBCy0o8Rc3wRMwARMwAQGCFhoB2C5qgmYgAmYgAmMErDQjhJzfRMwARMwARMYIPAf0qpwRCQqIAAAAAAASUVORK5CYII=\" width=\"474\" height=\"66\"\u003e\u003c/p\u003e\n\u003cp\u003eWhere \u003cem\u003eM\u003csub\u003et\u003c/sub\u003e\u003c/em\u003e is the uptake (g) at time \u003cem\u003et\u003c/em\u003e, \u003cem\u003eM\u003csub\u003esat\u003c/sub\u003e\u003c/em\u003e is the uptake (g) at infinite time (i.e., at equilibrium), \u003cem\u003eD\u003c/em\u003e has units of m\u003csup\u003e2\u003c/sup\u003e/s, and \u003cem\u003el\u003c/em\u003e is the film thickness. Following the W\u0026ouml;ll and coworkers report,\u003csup\u003e43\u003c/sup\u003e the above equation can be expressed as following:\u003c/p\u003e\n\u003cp\u003e\u003cimg src=\"data:image/png;base64,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\" height=\"179\" width=\"662\"\u003e\u003c/p\u003e\n\u003cp\u003e\u003cem\u003eD\u003c/em\u003e is calculated using the \u003cem\u003e\u0026tau;\u003c/em\u003e value, obtained by fitting equation 3.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMolecular dynamics simulation\u003c/strong\u003e:\u003c/p\u003e\n\u003cp\u003eAt first, the corresponding superstructure is generated from the unit cell of the Cu(bdc)(azbpy) MOF spanning along 3*3*6 dimensions. We have considered two situations with the superstructure framework extended as 3*3*6 (in x, y, z directions respectively) considering : I) high concentration gradient, i.e MOF thin film pores are almost empty (containing only one molecule of each of the alkanes, 1BP and 2BP in the framework), II) low concentration gradient, i.e. ~20% (of saturation amount) filled pores (including multiple molecules of each type of alkane at a time, i.e. 11 molecules of 1BP and 9 molecules of 2BP corresponding to the respective number of molecular uptakes at ~20% loading). Initially, in both the cases molecular dynamics simulation is performed by freezing the MOF (utilizing \u0026lsquo;freeze group\u0026rsquo; utility installed in gromacs) as we\u0026nbsp;anticipated only adsorbent-adsorbate interaction driven diffusivity trends. The partial charges over the atoms of MOF are obtained from the quantum calculations (see below)\u0026nbsp;and the alkane molecules are modeled using charmm36 force field parameters.\u003csup\u003e58-60\u003c/sup\u003e Each of the simulation both in high and low concentration gradient for each of the haloalkane molecules are performed in gas phase. The entire system was packed in a rectangular box of dimension 3.26 \u0026times; 3.26 \u0026times; 9.54 nm\u003csup\u003e3\u003c/sup\u003e as per the resultant dimension of the superstructure.\u003c/p\u003e\n\u003cp\u003eFurther, the similar set of simulations was performed in flexible framework. The respective bond, angle and dihedral parameters of the MOF were obtained using obgmx tool and the partial charges were kept unaltered as the set of the previous simulations performed excluding framework dynamics were excluded.\u003c/p\u003e\n\u003cp\u003eTo realize the effect of bromine substitution in MOF on the haloalkane isomer selectivity, Cu(Br\u003csub\u003e2\u003c/sub\u003e-bdc)(azbpy) has been simulated under the condition of high concentration gradient, i.e MOF thin film pores are almost empty (containing only one molecule of each of the alkanes, 1BP and 2BP in the framework). The simulations in brominated MOF for each of the haloalkane were carried out in flexible framework arrangement where the partial charges of MOF were obtained from the similar quantum calculation (see below) and the bond, angle and dihedrals parameters from obgmx. The alkanes were modeled with charmm36 parameters as utilized before. The dimension of the simulation box was kept fixed corresponding to the similar dimension of the MOF superstructure build along the direction of 3*3*6 (corresponding to x, y and z directions respectively).\u003c/p\u003e\n\u003cp\u003eSimulation method\u003cstrong\u003e:\u003c/strong\u003e Each of the simulation is performed using periodic boundary conditions (PBC) set in all three dimensions. Long-range electrostatic interactions were maintained employing the particle mesh Ewald (PME) method\u003csup\u003e61\u003c/sup\u003e with cubic interpolation. For the electrostatic interactions at short-range, the cut-off of 1.2 nm was employed. During freezed framework simulation of the Cu(bdc)(azbpy), the MOF dynamics was excluded using \u0026ldquo; freeze group\u0026rdquo; utility of gromacs. Otherwise for the alkane molecules in the freezed system and the MOF along with alkanes in the flexible framework system, for constraining each \u0026nbsp;the bonds involving hydrogen atoms, the LINCS algorithm\u003csup\u003e62\u003c/sup\u003e was applied. At first, the system was energy minimized with the steepest-decent algorithm followed by stepwise equilibration in seven successive steps with gradual increase of temperature (in an interval of 50 K starting from 50 K upto 300 K) of 100 ps each (with time step of 0.0005 ps). During equilibration, the average temperature was kept fixed at the corresponding temperatures by using V-rescale thermostat via coupling the MOF and the alkane molecules separately. Finally, the equilibrated system was subjected to NVT production run for 10 nanosecond. During production simulation also, the average temperature of 300 K was maintained with the help of same V-rescale thermostat. To execute all simulations GROMACS software of version 20x were utilized.\u003c/p\u003e\n\u003cp\u003eThe diffusion phenomenon of the haloalkane molecules were inspected by calculating mean square displacement (msd) utilizing the tool of \u0026ldquo;gmx msd\u0026rdquo; and the corresponding diffusion coefficient (\u003cem\u003eD\u003c/em\u003e) were approximated. To understand the mode of chemical interactions of the haloalkane molecules with the different parts of the MOF pair correlation function of the alkane moieties (whole molecule, bromine atom and the C\u0026alpha; carbon of the alkane molecule linked to the bromine group) were measured with respect to the specific parts of the MOF (i.e. \u0026ndash;N=N-, pyridyl and bdc).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAb initio Molecular Dynamic Simulation\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll AIMD simulations were run using CP2K software\u003csup\u003e63\u003c/sup\u003e (version 9.1) with PBE functional\u003csup\u003e64\u003c/sup\u003e and each MD time step of 0.5 fs at 300 K. The dimensions of the cell with periodic boundary conditions were 10.886 \u0026Aring;, 10.886 \u0026Aring;, and 15.9041 \u0026Aring;. The valence electrons of H, C, N, and O atoms were modelled with DZVP-GTH basis sets whereas DZVP-MOLOPT-SR-GTH basis set was employed for Br and Cu centers. The core electrons of all the atoms were modelled using GTH-PBE pseudopotentials. All NVT simulations employed Nose-Hoover chain thermostatting.\u003csup\u003e65-67\u003c/sup\u003e For the self-diffusion studies, NVT simulations were run for 50 ps. The analysis of the probability distribution of Br (2BP and 1BP) - C (bdc linker) distance involved data collected at an interval of 5 fs during the crossing of the molecule across the pore (1BP: 12.5 ps \u0026ndash; 17.5 ps; 2BP: 25 ps \u0026ndash; 29 ps) surrounded by the bdc molecules. The MSDs were computed with freud code.\u003csup\u003e68\u003c/sup\u003e The calculation of the diffusion constant was done by linear fitting of the MSD data (between 12.5-17.5ps for 1BP and 22-28ps for 2BP).\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAuthor contribution\u003c/strong\u003e: T.M, R.H conceived the idea and planned the experiments, T. M did the synthesis, measurements and analysis with guidance from R.H, S.K and S.P helped with the characterizations, A.S and K.M helped with the HPLC measurements, S.S did the MD simulation with guidance from J.M, S.G did AIMD simulation, manuscript draft was prepared with the inputs from all the authors.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgement\u003c/strong\u003e: R.H acknowledges the financial support from the Science and Engineering Research Board (SERB), Govt. of India (Project No: SRG/2022/000927), all the authors acknowledge the intramural funds at TIFR Hyderabad from the Department of Atomic Energy (DAE), India, under Project Identification Number RTI 4007. We are grateful to Prof. S. Balasubramanian (JNCASR, India) for a very helpful discussion on the MD simulation.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eLi, Y. \u0026amp; Yu, J. Emerging applications of zeolites in catalysis, separation and host\u0026ndash;guest assembly. \u003cem\u003eNature Reviews Materials\u003c/em\u003e \u003cstrong\u003e6\u003c/strong\u003e, 1156-1174 (2021). \u003c/li\u003e\n\u003cli\u003eFurukawa, H., Cordova, K. E., O\u0026rsquo;Keeffe, M. \u0026amp; Yaghi, O. M. The Chemistry and Applications of Metal-Organic Frameworks. \u003cem\u003eScience\u003c/em\u003e \u003cstrong\u003e341\u003c/strong\u003e, 1230444 (2013). \u003c/li\u003e\n\u003cli\u003eKitagawa, S., Kitaura, R. \u0026amp; Noro, S.-i. Functional Porous Coordination Polymers. \u003cem\u003eAngewandte Chemie International Edition\u003c/em\u003e \u003cstrong\u003e43\u003c/strong\u003e, 2334-2375 (2004). \u003c/li\u003e\n\u003cli\u003eGeng, K.\u003cem\u003e et al.\u003c/em\u003e Covalent Organic Frameworks: Design, Synthesis, and Functions. \u003cem\u003eChemical Reviews\u003c/em\u003e \u003cstrong\u003e120\u003c/strong\u003e, 8814-8933 (2020). \u003c/li\u003e\n\u003cli\u003eKitagawa, S. Future Porous Materials. \u003cem\u003eAccounts of Chemical Research\u003c/em\u003e \u003cstrong\u003e50\u003c/strong\u003e, 514-516 (2017). \u003c/li\u003e\n\u003cli\u003eFoo, M. L., Matsuda, R. \u0026amp; Kitagawa, S. Functional Hybrid Porous Coordination Polymers. \u003cem\u003eChemistry of Materials\u003c/em\u003e \u003cstrong\u003e26\u003c/strong\u003e, 310-322 (2014). \u003c/li\u003e\n\u003cli\u003eSholl, D. S. \u0026amp; Lively, R. P. Seven chemical separations to change the world. \u003cem\u003eNature\u003c/em\u003e \u003cstrong\u003e532\u003c/strong\u003e, 435-437 (2016). \u003c/li\u003e\n\u003cli\u003eKnebel, A. \u0026amp; Caro, J. Metal\u0026ndash;organic frameworks and covalent organic frameworks as disruptive membrane materials for energy-efficient gas separation. \u003cem\u003eNature Nanotechnology\u003c/em\u003e \u003cstrong\u003e17\u003c/strong\u003e, 911-923 (2022). \u003c/li\u003e\n\u003cli\u003eQian, Q.\u003cem\u003e et al.\u003c/em\u003e MOF-Based Membranes for Gas Separations. \u003cem\u003eChemical Reviews\u003c/em\u003e \u003cstrong\u003e120\u003c/strong\u003e, 8161-8266 (2020). \u003c/li\u003e\n\u003cli\u003ePeng, P., Gao, X.-H., Yan, Z.-F. \u0026amp; Mintova, S. Diffusion and catalyst efficiency in hierarchical zeolite catalysts. \u003cem\u003eNational Science Review\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 1726-1742 (2020). \u003c/li\u003e\n\u003cli\u003eDong, B.\u003cem\u003e et al.\u003c/em\u003e Deciphering nanoconfinement effects on molecular orientation and reaction intermediate by single molecule imaging. \u003cem\u003eNature Communications\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 4815 (2019). \u003c/li\u003e\n\u003cli\u003eSharp, C. H.\u003cem\u003e et al.\u003c/em\u003e Nanoconfinement and mass transport in metal\u0026ndash;organic frameworks. \u003cem\u003eChemical Society Reviews\u003c/em\u003e \u003cstrong\u003e50\u003c/strong\u003e, 11530-11558 (2021). \u003c/li\u003e\n\u003cli\u003eZ\u0026uuml;rner, A., Kirstein, J., D\u0026ouml;blinger, M., Br\u0026auml;uchle, C. \u0026amp; Bein, T. Visualizing single-molecule diffusion in mesoporous materials. \u003cem\u003eNature\u003c/em\u003e \u003cstrong\u003e450\u003c/strong\u003e, 705-708 (2007). \u003c/li\u003e\n\u003cli\u003eK\u0026auml;rger, J. \u0026amp; Ruthven, D. M. Diffusion in nanoporous materials: fundamental principles, insights and challenges. \u003cem\u003eNew Journal of Chemistry\u003c/em\u003e \u003cstrong\u003e40\u003c/strong\u003e, 4027-4048 (2016). \u003c/li\u003e\n\u003cli\u003eLi, J.-R., Kuppler, R. J. \u0026amp; Zhou, H.-C. Selective gas adsorption and separation in metal\u0026ndash;organic frameworks. \u003cem\u003eChemical Society Reviews\u003c/em\u003e \u003cstrong\u003e38\u003c/strong\u003e, 1477-1504 (2009). \u003c/li\u003e\n\u003cli\u003eSumida, K.\u003cem\u003e et al.\u003c/em\u003e Carbon Dioxide Capture in Metal\u0026ndash;Organic Frameworks. \u003cem\u003eChemical Reviews\u003c/em\u003e \u003cstrong\u003e112\u003c/strong\u003e, 724-781 (2012). \u003c/li\u003e\n\u003cli\u003eLustig, W. P.\u003cem\u003e et al.\u003c/em\u003e Metal\u0026ndash;organic frameworks: functional luminescent and photonic materials for sensing applications. \u003cem\u003eChemical Society Reviews\u003c/em\u003e \u003cstrong\u003e46\u003c/strong\u003e, 3242-3285 (2017). \u003c/li\u003e\n\u003cli\u003eYang, D. \u0026amp; Gates, B. C. Catalysis by Metal Organic Frameworks: Perspective and Suggestions for Future Research. \u003cem\u003eACS Catalysis\u003c/em\u003e \u003cstrong\u003e9\u003c/strong\u003e, 1779-1798 (2019). \u003c/li\u003e\n\u003cli\u003eBavykina, A.\u003cem\u003e et al.\u003c/em\u003e Metal\u0026ndash;Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives. \u003cem\u003eChemical Reviews\u003c/em\u003e \u003cstrong\u003e120\u003c/strong\u003e, 8468-8535 (2020). \u003c/li\u003e\n\u003cli\u003eLiu, G.\u003cem\u003e et al.\u003c/em\u003e Eliminating lattice defects in metal\u0026ndash;organic framework molecular-sieving membranes. \u003cem\u003eNature Materials\u003c/em\u003e \u003cstrong\u003e22\u003c/strong\u003e, 769-776 (2023). \u003c/li\u003e\n\u003cli\u003eYu, X.-J.\u003cem\u003e et al.\u003c/em\u003e Liquid-Phase Epitaxial Growth of Highly Oriented and Multivariate Surface-Attached Metal\u0026ndash;Organic Frameworks. \u003cem\u003eJournal of the American Chemical Society\u003c/em\u003e \u003cstrong\u003e141\u003c/strong\u003e, 18984-18993 (2019). \u003c/li\u003e\n\u003cli\u003eLi, S., Chung, Y. G., Simon, C. M. \u0026amp; Snurr, R. Q. High-Throughput Computational Screening of Multivariate Metal\u0026ndash;Organic Frameworks (MTV-MOFs) for CO2 Capture. \u003cem\u003eThe Journal of Physical Chemistry Letters\u003c/em\u003e \u003cstrong\u003e8\u003c/strong\u003e, 6135-6141 (2017). \u003c/li\u003e\n\u003cli\u003eListyarini, R. V., Gamper, J. \u0026amp; Hofer, T. S. Storage and Diffusion of Carbon Dioxide in the Metal Organic Framework MOF-5─A Semi-empirical Molecular Dynamics Study. \u003cem\u003eThe Journal of Physical Chemistry B\u003c/em\u003e \u003cstrong\u003e127\u003c/strong\u003e, 9378-9389 (2023). \u003c/li\u003e\n\u003cli\u003eSkoulidas, A. I. Molecular Dynamics Simulations of Gas Diffusion in Metal\u0026minus;Organic Frameworks:\u0026thinsp; Argon in CuBTC. \u003cem\u003eJournal of the American Chemical Society\u003c/em\u003e \u003cstrong\u003e126\u003c/strong\u003e, 1356-1357 (2004). \u003c/li\u003e\n\u003cli\u003eFormalik, F., Shi, K., Joodaki, F., Wang, X. \u0026amp; Snurr, R. Q. Exploring the Structural, Dynamic, and Functional Properties of Metal-Organic Frameworks through Molecular Modeling. \u003cem\u003eAdvanced Functional Materials\u003c/em\u003e \u003cstrong\u003en/a\u003c/strong\u003e, 2308130 \u003c/li\u003e\n\u003cli\u003eAzar, A. N. V., Velioglu, S. \u0026amp; Keskin, S. Large-Scale Computational Screening of Metal Organic Framework (MOF) Membranes and MOF-Based Polymer Membranes for H2/N2 Separations. \u003cem\u003eACS Sustainable Chemistry \u0026amp; Engineering\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 9525-9536 (2019). \u003c/li\u003e\n\u003cli\u003eDaglar, H. \u0026amp; Keskin, S. High-Throughput Screening of Metal Organic Frameworks as Fillers in Mixed Matrix Membranes for Flue Gas Separation. \u003cem\u003eAdvanced Theory and Simulations\u003c/em\u003e \u003cstrong\u003e2\u003c/strong\u003e, 1900109 (2019). \u003c/li\u003e\n\u003cli\u003eSikdar, N., Bhogra, M., Waghmare, Umesh V. \u0026amp; Maji, T. K. Oriented attachment growth of anisotropic meso/nanoscale MOFs: tunable surface area and CO2 separation. \u003cem\u003eJournal of Materials Chemistry A\u003c/em\u003e \u003cstrong\u003e5\u003c/strong\u003e, 20959-20968 (2017). \u003c/li\u003e\n\u003cli\u003eMalik, P. \u0026amp; Haldar, R. Accessing accelerated molecular diffusion by nanopore alignment in a MOF thin film. \u003cem\u003eMolecular Systems Design \u0026amp; Engineering\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 873-877 (2022). \u003c/li\u003e\n\u003cli\u003eDatta, S. J.\u003cem\u003e et al.\u003c/em\u003e Rational design of mixed-matrix metal-organic framework membranes for molecular separations. \u003cem\u003eScience\u003c/em\u003e \u003cstrong\u003e376\u003c/strong\u003e, 1080-1087 (2022). \u003c/li\u003e\n\u003cli\u003eWang, L.\u003cem\u003e et al.\u003c/em\u003e Aligned Metal\u0026ndash;Organic Framework Nanoplates in Mixed-Matrix Membranes for Highly Selective CO2/CH4 Separation. \u003cem\u003eAdvanced Materials Interfaces\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 2202524 (2023). \u003c/li\u003e\n\u003cli\u003eFan, H.\u003cem\u003e et al.\u003c/em\u003e MOF-in-COF molecular sieving membrane for selective hydrogen separation. \u003cem\u003eNature Communications\u003c/em\u003e \u003cstrong\u003e12\u003c/strong\u003e, 38 (2021). \u003c/li\u003e\n\u003cli\u003eKwon, H. T., Jeong, H.-K., Lee, A. S., An, H. S. \u0026amp; Lee, J. S. Heteroepitaxially Grown Zeolitic Imidazolate Framework Membranes with Unprecedented Propylene/Propane Separation Performances. \u003cem\u003eJournal of the American Chemical Society\u003c/em\u003e \u003cstrong\u003e137\u003c/strong\u003e, 12304-12311 (2015). \u003c/li\u003e\n\u003cli\u003eLi, W.\u003cem\u003e et al.\u003c/em\u003e Transformation of metal-organic frameworks for molecular sieving membranes. \u003cem\u003eNature Communications\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 11315 (2016). \u003c/li\u003e\n\u003cli\u003eSong, Z.\u003cem\u003e et al.\u003c/em\u003e Dual-Channel, Molecular-Sieving Core/Shell ZIF@MOF Architectures as Engineered Fillers in Hybrid Membranes for Highly Selective CO2 Separation. \u003cem\u003eNano Letters\u003c/em\u003e \u003cstrong\u003e17\u003c/strong\u003e, 6752-6758 (2017). \u003c/li\u003e\n\u003cli\u003eTonnah, R. K.\u003cem\u003e et al.\u003c/em\u003e Bioinspired Angstrom-Scale Heterogeneous MOF-on-MOF Membrane for Osmotic Energy Harvesting. \u003cem\u003eACS Nano\u003c/em\u003e \u003cstrong\u003e17\u003c/strong\u003e, 12445-12457 (2023). \u003c/li\u003e\n\u003cli\u003eMarshall, K. A.\u003cem\u003e et al.\u003c/em\u003e in \u003cem\u003eUllmann\u0026apos;s Encyclopedia of Industrial Chemistry\u003c/em\u003e 1-22.\u003c/li\u003e\n\u003cli\u003eHua, B.\u003cem\u003e et al.\u003c/em\u003e Tuning the porosity of triangular supramolecular adsorbents for superior haloalkane isomer separations. \u003cem\u003eChemical Science\u003c/em\u003e \u003cstrong\u003e12\u003c/strong\u003e, 12286-12291 (2021). \u003c/li\u003e\n\u003cli\u003eMaity, T.\u003cem\u003e et al.\u003c/em\u003e Chemically routed interpore molecular diffusion in metal-organic framework thin films. \u003cem\u003eNature Communications\u003c/em\u003e \u003cstrong\u003e14\u003c/strong\u003e, 2212 (2023). \u003c/li\u003e\n\u003cli\u003eShekhah, O.\u003cem\u003e et al.\u003c/em\u003e Step-by-Step Route for the Synthesis of Metal\u0026minus;Organic Frameworks. \u003cem\u003eJournal of the American Chemical Society\u003c/em\u003e \u003cstrong\u003e129\u003c/strong\u003e, 15118-15119 (2007). \u003c/li\u003e\n\u003cli\u003eChen, D.-H., Gliemann, H. \u0026amp; W\u0026ouml;ll, C. Layer-by-layer assembly of metal-organic framework thin films: Fabrication and advanced applications. \u003cem\u003eChemical Physics Reviews\u003c/em\u003e \u003cstrong\u003e4\u003c/strong\u003e (2023). \u003c/li\u003e\n\u003cli\u003eZybaylo, O.\u003cem\u003e et al.\u003c/em\u003e A novel method to measure diffusion coefficients in porous metal\u0026ndash;organic frameworks. \u003cem\u003ePhysical Chemistry Chemical Physics\u003c/em\u003e \u003cstrong\u003e12\u003c/strong\u003e, 8093-8098 (2010). \u003c/li\u003e\n\u003cli\u003eHeinke, L., Gu, Z. \u0026amp; W\u0026ouml;ll, C. The surface barrier phenomenon at the loading of metal-organic frameworks. \u003cem\u003eNature Communications\u003c/em\u003e \u003cstrong\u003e5\u003c/strong\u003e, 4562 (2014). \u003c/li\u003e\n\u003cli\u003eLing, Y.\u003cem\u003e et al.\u003c/em\u003e A zinc(ii) metal\u0026ndash;organic framework based on triazole and dicarboxylate ligands for selective adsorption of hexane isomers. \u003cem\u003eChemical Communications\u003c/em\u003e \u003cstrong\u003e47\u003c/strong\u003e, 7197-7199 (2011). \u003c/li\u003e\n\u003cli\u003eChen, B.\u003cem\u003e et al.\u003c/em\u003e A Microporous Metal\u0026ndash;Organic Framework for Gas-Chromatographic Separation of Alkanes. \u003cem\u003eAngewandte Chemie International Edition\u003c/em\u003e \u003cstrong\u003e45\u003c/strong\u003e, 1390-1393 (2006). \u003c/li\u003e\n\u003cli\u003eHenrique, A., Rodrigues, A. E. \u0026amp; Silva, J. A. C. Separation of Hexane Isomers in ZIF-8 by Fixed Bed Adsorption. \u003cem\u003eIndustrial \u0026amp; Engineering Chemistry Research\u003c/em\u003e \u003cstrong\u003e58\u003c/strong\u003e, 378-394 (2019). \u003c/li\u003e\n\u003cli\u003eXu, X., Cui, Q., Chen, H. \u0026amp; Huang, N. Carborane-Based Three-Dimensional Covalent Organic Frameworks. \u003cem\u003eJournal of the American Chemical Society\u003c/em\u003e \u003cstrong\u003e145\u003c/strong\u003e, 24202-24209 (2023). \u003c/li\u003e\n\u003cli\u003eHenrique, A.\u003cem\u003e et al.\u003c/em\u003e Hexane isomers separation on an isoreticular series of microporous Zr carboxylate metal organic frameworks. \u003cem\u003eJournal of Materials Chemistry A\u003c/em\u003e \u003cstrong\u003e8\u003c/strong\u003e, 17780-17789 (2020). \u003c/li\u003e\n\u003cli\u003eFerreira, A. F. P.\u003cem\u003e et al.\u003c/em\u003e Sieving di-branched from mono-branched and linear alkanes using ZIF-8: experimental proof and theoretical explanation. \u003cem\u003ePhysical Chemistry Chemical Physics\u003c/em\u003e \u003cstrong\u003e15\u003c/strong\u003e, 8795-8804 (2013). \u003c/li\u003e\n\u003cli\u003eVlugt, T. J. H.\u003cem\u003e et al.\u003c/em\u003e Adsorption of Linear and Branched Alkanes in the Zeolite Silicalite-1. \u003cem\u003eJournal of the American Chemical Society\u003c/em\u003e \u003cstrong\u003e120\u003c/strong\u003e, 5599-5600 (1998). \u003c/li\u003e\n\u003cli\u003eKrishna, R. \u0026amp; van Baten, J. M. Highlighting the Anti-Synergy between Adsorption and Diffusion in Cation-Exchanged Faujasite Zeolites. \u003cem\u003eACS Omega\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 13050-13056 (2022). \u003c/li\u003e\n\u003cli\u003eDeng, H.\u003cem\u003e et al.\u003c/em\u003e Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks. \u003cem\u003eScience\u003c/em\u003e \u003cstrong\u003e327\u003c/strong\u003e, 846-850 (2010). \u003c/li\u003e\n\u003cli\u003eDong, Z., Sun, Y., Chu, J., Zhang, X. \u0026amp; Deng, H. Multivariate Metal\u0026ndash;Organic Frameworks for Dialing-in the Binding and Programming the Release of Drug Molecules. \u003cem\u003eJournal of the American Chemical Society\u003c/em\u003e \u003cstrong\u003e139\u003c/strong\u003e, 14209-14216 (2017). \u003c/li\u003e\n\u003cli\u003eKo, S.\u003cem\u003e et al.\u003c/em\u003e Effect of Spatial Heterogeneity on the Unusual Uptake Behavior of Multivariate-Metal\u0026ndash;Organic Frameworks. \u003cem\u003eJournal of the American Chemical Society\u003c/em\u003e \u003cstrong\u003e145\u003c/strong\u003e, 3101-3107 (2023). \u003c/li\u003e\n\u003cli\u003eKong, X.\u003cem\u003e et al.\u003c/em\u003e Mapping of Functional Groups in Metal-Organic Frameworks. \u003cem\u003eScience\u003c/em\u003e \u003cstrong\u003e341\u003c/strong\u003e, 882-885 (2013). \u003c/li\u003e\n\u003cli\u003eLaunay, J. P., Tourrel-Pagis, M., Lipskier, J. F., Marvaud, V. \u0026amp; Joachim, C. Control of intramolecular electron transfer by a chemical reaction. The 4,4\u0026apos;-azopyridine/1,2-bis(4-pyridyl)hydrazine system. \u003cem\u003eInorganic Chemistry\u003c/em\u003e \u003cstrong\u003e30\u003c/strong\u003e, 1033-1038 (1991). \u003c/li\u003e\n\u003cli\u003eWannapaiboon, S.\u003cem\u003e et al.\u003c/em\u003e Control of structural flexibility of layered-pillared metal-organic frameworks anchored at surfaces. \u003cem\u003eNature Communications\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 346 (2019). \u003c/li\u003e\n\u003cli\u003eHuang, J.\u003cem\u003e et al.\u003c/em\u003e CHARMM36m: an improved force field for folded and intrinsically disordered proteins. \u003cem\u003eNature Methods\u003c/em\u003e \u003cstrong\u003e14\u003c/strong\u003e, 71-73 (2017). \u003c/li\u003e\n\u003cli\u003eKlauda, J. B.\u003cem\u003e et al.\u003c/em\u003e Update of the CHARMM All-Atom Additive Force Field for Lipids: Validation on Six Lipid Types. \u003cem\u003eThe Journal of Physical Chemistry B\u003c/em\u003e \u003cstrong\u003e114\u003c/strong\u003e, 7830-7843 (2010). \u003c/li\u003e\n\u003cli\u003eBrooks, B. R.\u003cem\u003e et al.\u003c/em\u003e CHARMM: The biomolecular simulation program. \u003cem\u003eJournal of Computational Chemistry\u003c/em\u003e \u003cstrong\u003e30\u003c/strong\u003e, 1545-1614 (2009). \u003c/li\u003e\n\u003cli\u003eDarden, T., York, D. \u0026amp; Pedersen, L. Particle mesh Ewald: An N\u0026sdot;log(N) method for Ewald sums in large systems. \u003cem\u003eThe Journal of Chemical Physics\u003c/em\u003e \u003cstrong\u003e98\u003c/strong\u003e, 10089-10092 (1993). \u003c/li\u003e\n\u003cli\u003eHess, B., Bekker, H., Berendsen, H. J. C. \u0026amp; Fraaije, J. G. E. M. LINCS: A linear constraint solver for molecular simulations. \u003cem\u003eJournal of Computational Chemistry\u003c/em\u003e \u003cstrong\u003e18\u003c/strong\u003e, 1463-1472 (1997). \u003c/li\u003e\n\u003cli\u003eK\u0026uuml;hne, T. D.\u003cem\u003e et al.\u003c/em\u003e CP2K: An electronic structure and molecular dynamics software package - Quickstep: Efficient and accurate electronic structure calculations. \u003cem\u003eThe Journal of Chemical Physics\u003c/em\u003e \u003cstrong\u003e152\u003c/strong\u003e (2020). \u003c/li\u003e\n\u003cli\u003ePerdew, J. P., Burke, K. \u0026amp; Ernzerhof, M. Generalized Gradient Approximation Made Simple. \u003cem\u003ePhysical Review Letters\u003c/em\u003e \u003cstrong\u003e77\u003c/strong\u003e, 3865-3868 (1996). \u003c/li\u003e\n\u003cli\u003eNos\u0026eacute;, S. A unified formulation of the constant temperature molecular dynamics methods. \u003cem\u003eThe Journal of Chemical Physics\u003c/em\u003e \u003cstrong\u003e81\u003c/strong\u003e, 511-519 (1984). \u003c/li\u003e\n\u003cli\u003eMartyna, G. J., Klein, M. L. \u0026amp; Tuckerman, M. Nos\u0026eacute;\u0026ndash;Hoover chains: The canonical ensemble via continuous dynamics. \u003cem\u003eThe Journal of Chemical Physics\u003c/em\u003e \u003cstrong\u003e97\u003c/strong\u003e, 2635-2643 (1992). \u003c/li\u003e\n\u003cli\u003eHoover, W. G. Canonical dynamics: Equilibrium phase-space distributions. \u003cem\u003ePhysical Review A\u003c/em\u003e \u003cstrong\u003e31\u003c/strong\u003e, 1695-1697 (1985). \u003c/li\u003e\n\u003cli\u003eRamasubramani, V.\u003cem\u003e et al.\u003c/em\u003e freud: A software suite for high throughput analysis of particle simulation data. \u003cem\u003eComputer Physics Communications\u003c/em\u003e \u003cstrong\u003e254\u003c/strong\u003e, 107275 (2020). \u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-4046811/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4046811/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"The movement of molecules (i.e. diffusion) within angstrom-scale pores of porous materials such as metal-organic frameworks (MOFs) and zeolites is influenced by multiple complex factors that can be challenging to assess and manipulate. Nevertheless, understanding and controlling this diffusion phenomenon is crucial for advancing energy-economic membrane-based chemical separation technologies, as well as for heterogeneous catalysis and sensing applications. Through precise assessment of the factors influencing diffusion within a porous metal-organic framework (MOF) thin film, we have developed a chemical strategy to manipulate and reverse chemical isomer diffusion selectivity. In the process of cognizing the molecular diffusion within oriented, angstrom-scale channels of MOF thin film, we have unveiled a dynamic chemical interaction between the adsorbate (chemical isomers) and the MOF using a combination of kinetic mass uptake experiments and molecular simulation. Leveraging the dynamic chemical interactions, we have reversed the haloalkane (positional) isomer diffusion selectivity, forging a novel chemical pathway to elevate the overall efficacy of membrane-based chemical separation and selective catalytic reactions.","manuscriptTitle":"Steering diffusion selectivity of chemical isomers within aligned nanochannels of metal-organic framework thin film","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-03-21 10:58:44","doi":"10.21203/rs.3.rs-4046811/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"9c84c351-a721-40a0-ae80-59d05bd0ca85","owner":[],"postedDate":"March 21st, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":29676983,"name":"Physical sciences/Chemistry/Materials chemistry/Metal\u0026#x2013;organic frameworks"},{"id":29676984,"name":"Physical sciences/Materials science/Materials for energy and catalysis/Metal\u0026#x2013;organic frameworks"}],"tags":[],"updatedAt":"2024-11-09T08:07:10+00:00","versionOfRecord":{"articleIdentity":"rs-4046811","link":"https://doi.org/10.1038/s41467-024-53207-3","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2024-11-08 05:00:00","publishedOnDateReadable":"November 8th, 2024"},"versionCreatedAt":"2024-03-21 10:58:44","video":"","vorDoi":"10.1038/s41467-024-53207-3","vorDoiUrl":"https://doi.org/10.1038/s41467-024-53207-3","workflowStages":[]},"version":"v1","identity":"rs-4046811","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4046811","identity":"rs-4046811","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}