Scalable fabrication of COF membranes for aliphatic/aromatic separation of crude oil
Data files
Jun 10, 2026 version files 7.62 MB
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Fig_2.xlsx
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Fig_3.xlsx
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Fig_S10.xlsx
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Fig_S16.xlsx
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Fig_S17.xlsx
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Fig_S18.xlsx
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Fig_S2.xlsx
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Fig_S24.xlsx
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Fig_S25.xlsx
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Fig_S26.xlsx
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Fig_S27.xlsx
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Fig_S28.xlsx
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Fig_S44.xlsx
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Fig_S47.xlsx
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Fig_S5.xlsx
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Fig_S7.xlsx
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README.md
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Abstract
Distillation has been the cornerstone of crude oil refining for over a century, relying on boiling point differences for fractionation. While effective, it is highly energy-intensive and lacks the precision to separate specific hydrocarbon classes. We report crystalline covalent organic framework (COF) membranes with well-defined micropores and alkyl-functionalized frameworks that combine molecular sieving with preferential affinity to enrich aliphatics. An electric-field-assisted roll-to-roll process enabled scalable fabrication of continuous membranes. These COF membranes enriched aliphatics to >95% and delivered permeance orders of magnitude higher than amorphous polymers in real Arabian Light crude oil. A crude oil permeance of 0.34 L m⁻² h⁻¹ bar⁻¹ with >90% aliphatics enrichment was achieved using industrial-standard 1812 membrane modules, demonstrating a lower energy demand than distillation.
Dataset DOI: 10.5061/dryad.dr7sqvbd5
Description of the data and file structure
This file contains XRD profiles of COF-Me, COF-But, and COF-Hex membranes with AA and ABC stacking models, as well as XRD profiles of COF-But membranes fabricated under different conditions, including varied pre-polymerization times and electric field strengths. It also includes simulated XRD patterns of COF-Me, COF-But, and COF-Hex, chemical structure characterization data such as FT-IR and ¹³C NMR spectra, porosity characterization results of COF-Me, COF-But, and COF-Hex membranes, and crystalline structure changes of COF membranes in solvents. These measurements were conducted at the KAUST Core Labs and IRM Lab.
Files and variables
File: Fig_2.xlsx
Description: This file contains the data for Fig. 2F, G, H, and K in the main text. The data were collected using a Bruker D8 Eiger system and a Bruker D8 Twin diffractometer. Fig. 2F, G, and H show the XRD patterns of three COF membranes, the corresponding COF powder samples, and the simulated XRD patterns. Molecular modeling of the COFs was performed using the Materials Studio software suite, version 2020. Pawley refinement was conducted using the Reflex module, which enables crystal structure determination from powder X-ray diffraction (PXRD) data. The unit cell dimensions were initially set to the theoretical values, and the refinement was iteratively optimized to minimize the weighted profile R-factor (Rwp), ensuring good agreement between the observed and calculated diffraction patterns. These XRD results demonstrate that the synthesized COF membranes adopt an ABC stacking model, consistent with the simulated results. “2θ” is the angle between the incident X-ray beam and the diffracted X-ray beam, with the unit of degree. “Pawley Refined” refers to the calculated XRD pattern obtained from Pawley refinement. “Difference” is the residual curve, defined as Difference = Iobserved − Icalculated, which shows the deviation between the refined and experimental XRD patterns. “Bragg position” marks the expected diffraction peak positions of the refined crystal lattice. “Experimental Powder” refers to the XRD pattern collected from the powder samples. “ABC Stacking” refers to the simulated XRD pattern based on the ABC stacking model. “COF-Me, COF-But, and COF-Hex membranes” refer to the synthesized membrane samples.
Sheet K shows the XRD profiles of the pristine dry COF-But membrane, the COF-But membrane immersed in organic solvents, and the re-dried COF-But membrane. “2θ” is the angle between the incident X-ray beam and the diffracted X-ray beam, with the unit of degree. The columns labeled “COF-But membrane (Dry)”, “COF-But (Wet)”, and “COF-But (Redry)” indicate the XRD intensities of the three membrane samples. These data were collected using a Bruker D8 Eiger system.
File: Fig_3.xlsx
Description: This file contains the XRD patterns for Fig. 3G in the main text. The data were collected using a Bruker D8 Eiger system. The XRD patterns show COF-But membranes fabricated under different conditions. “2θ” is the angle between the incident X-ray beam and the diffracted X-ray beam, with the unit of degree. “COF-But-0.5h”, “COF-But-1h”, “COF-But-1.5h”, and “COF-But-2h” indicate the XRD intensities of COF-But membranes fabricated with prepolymerization times of 0.5, 1, 1.5, and 2 h, respectively.
File: Fig_S5.xlsx
Description: This file contains the XRD pattern for Fig. S5 in the supplementary materials. The data were collected using a Bruker D8 Eiger system. The XRD pattern indicates that the COF-Oct membrane is amorphous. “2θ” is the angle between the incident X-ray beam and the diffracted X-ray beam, with the unit of degree. “COF-Oct membrane” indicates the XRD intensity of the COF-Oct membrane.
File: Fig_S2.xlsx
Description: This file contains the XRD patterns for Fig. S2 in the supplementary materials. The data were collected using a Bruker D8 Eiger system and a Bruker D8 Twin diffractometer. These XRD patterns correspond to COF membranes with an AA stacking model. “2θ” is the angle between the incident X-ray beam and the diffracted X-ray beam, with the unit of degree. “COF-Me-AA powder/membrane”, “COF-But-AA powder/membrane”, and “COF-Oct-AA powder/membrane” indicate the XRD intensities of COF-Me-AA, COF-But-AA, and COF-Oct-AA in powder and membrane forms.
File: Fig_S18.xlsx
Description: This file contains FT-IR data (Sheet B) and ss ¹³C CP-NMR data (Sheet C) for Fig. S18. FT-IR spectra of the monomers and membranes were recorded on a Nicolet iS10 FT-IR spectrometer equipped with an ATR accessory. The wavenumber range is 600–4000 cm⁻¹. Solid-state ¹³C NMR spectra of the free-standing membranes were recorded on a Bruker 600M WB NMR spectrometer. The free-standing membranes were obtained by dissolving the PAN support in DMF. “Wavenumber” indicates the energy/frequency of infrared light absorbed by molecular bonds, with the unit of cm⁻¹. “Transmittance” describes the amount of IR light passing through the sample, with the unit of %. “Transmittance” in columns B, D, and F indicates the transmittance of the COF monomer PDA-Hex, TAPB-Et, and COF-Hex, respectively. “Chemical shift” indicates the resonance position of ¹³C nuclei in a magnetic field, with the unit of ppm. “Intensity” refers to the strength or height/area of the NMR signal, with the unit of a.u.
File: Fig_S16.xlsx
Description: This file contains Fourier-transform infrared spectroscopy (FT-IR) data (Sheet B) and solid-state ¹³C cross-polarization nuclear magnetic resonance (ss ¹³C CP-NMR) data (Sheet C) for Fig. S16. FT-IR spectra of the monomers and membranes were recorded on a Nicolet iS10 FT-IR spectrometer equipped with an attenuated total reflection (ATR) accessory. The wavenumber range is 600–4000 cm⁻¹. Solid-state ¹³C NMR spectra of the free-standing membranes were recorded on a Bruker 600M WB NMR spectrometer. The free-standing membranes were obtained by dissolving the PAN support in DMF. “Wavenumber” indicates the energy/frequency of infrared light absorbed by molecular bonds, with the unit of cm⁻¹. “Transmittance” describes the amount of IR light passing through the sample, with the unit of %. “Transmittance” in columns B, D, and F indicates the transmittance of the COF monomer PDA-Me, TAPB-Et, and COF-Me, respectively. “Chemical shift” indicates the resonance position of ¹³C nuclei in a magnetic field, with the unit of ppm. “Intensity” refers to the strength or height/area of the NMR signal, with the unit of a.u.
File: Fig_S17.xlsx
Description: This file contains FT-IR data (Sheet B) and ss ¹³C CP-NMR data (Sheet C) for Fig. S17. FT-IR spectra of the monomers and membranes were recorded on a Nicolet iS10 FT-IR spectrometer equipped with an ATR accessory. The wavenumber range is 600–4000 cm⁻¹. Solid-state ¹³C NMR spectra of the free-standing membranes were recorded on a Bruker 600M WB NMR spectrometer. The free-standing membranes were obtained by dissolving the PAN support in DMF. “Wavenumber” indicates the energy/frequency of infrared light absorbed by molecular bonds, with the unit of cm⁻¹. “Transmittance” describes the amount of IR light passing through the sample, with the unit of %. “Transmittance” in columns B, D, and F indicates the transmittance of the COF monomer PDA-But, TAPB-Et, and COF-But, respectively. “Chemical shift” indicates the resonance position of ¹³C nuclei in a magnetic field, with the unit of ppm. “Intensity” refers to the strength or height/area of the NMR signal, with the unit of a.u.
File: Fig_S24.xlsx
Description: This file contains the XRD patterns for Fig. S24 in the supplementary materials, showing the calculated and experimental PXRD profiles of three COFs with different stacking modes. The experimental data were collected using a Bruker D8 Twin diffractometer. Molecular modeling of the COFs was performed using the Materials Studio software suite, version 2020. “2θ” is the angle between the incident X-ray beam and the diffracted X-ray beam, with the unit of degree. “Experimental” indicates the XRD intensities of the synthesized COF-Me, COF-But, and COF-Hex powder samples, with the unit of a.u. “ABC stacking” indicates the XRD intensity of the simulated ABC stacking model, with the unit of a.u. “AB stacking” indicates the XRD intensity of the simulated AB stacking model, with the unit of a.u. “AA stacking” indicates the XRD intensity of the simulated AA stacking model, with the unit of a.u.
File: Fig_S7.xlsx
Description: This file contains the XRD pattern for Fig. S7 in the supplementary materials. The data were collected using a Bruker D8 Eiger system. The XRD pattern corresponds to a COF-But membrane fabricated with 30 min of prepolymerization followed by 30 min of deposition under an electric field of 10 V cm⁻¹. “2θ” is the angle between the incident X-ray beam and the diffracted X-ray beam, with the unit of degree. “Intensity” indicates the XRD intensity of the COF-But membrane, with the unit of a.u. These data are the same as those described in Fig. 3G.
File: Fig_S10.xlsx
Description: This file contains the XRD patterns for Fig. S10 in the supplementary materials. The data were collected using a Bruker D8 Eiger system. The XRD patterns show COF-But membranes fabricated under different conditions. “2θ” is the angle between the incident X-ray beam and the diffracted X-ray beam, with the unit of degree. “Pre-polymerization for 2 h and deposition for 30 min under 0 V cm⁻¹”, “Pre-polymerization for 2 h and deposition for 30 min under 5 V cm⁻¹”, and “Pre-polymerization for 2 h and deposition for 30 min under 20 V cm⁻¹” indicate the XRD intensities of COF-But membranes fabricated under electric fields of 0, 5, and 20 V cm⁻¹, respectively, with the unit of a.u.
File: Fig_S26.xlsx
Description: This file contains the nitrogen adsorption data for Fig. S26 in the supplementary materials. N₂ adsorption–desorption isotherms of free-standing amorphous COF-But membranes were measured at 77 K. Nitrogen sorption isotherms were obtained using a Micromeritics ASAP 2420 surface area and pore size analyzer. BET surface areas were calculated from the linear region of the N₂ isotherm within the relative pressure (P/P₀) range of 0.04–0.2. “Relative pressure (P/P₀)” is the ratio between the actual nitrogen gas pressure and the saturated vapor pressure of nitrogen at the measurement temperature; it is dimensionless. “Quantity adsorbed” indicates the amount of nitrogen gas adsorbed by the material at a given relative pressure, with the unit of cm³ g⁻¹ STP.
File: Fig_S25.xlsx
Description: This file contains the nitrogen adsorption data for Fig. S25 in the supplementary materials. N₂ adsorption–desorption isotherms of free-standing COF-Me, COF-But, and COF-Hex membranes were measured at 77 K. Nitrogen sorption isotherms were obtained using a Micromeritics ASAP 2420 surface area and pore size analyzer. Brunauer–Emmett–Teller (BET) surface areas were calculated from the linear region of the N₂ isotherm within the relative pressure (P/P₀) range of 0.04–0.2. “Relative pressure (P/P₀)” is the ratio between the actual nitrogen gas pressure and the saturated vapor pressure of nitrogen at the measurement temperature; it is dimensionless. “Quantity adsorbed” indicates the amount of nitrogen gas adsorbed by the material at a given relative pressure, with the unit of cm³ g⁻¹ STP.
File: Fig_S27.xlsx
Description: This file contains the XRD profiles for Fig. S27 in the supplementary materials. The data show the XRD patterns of the pristine dry COF-Me membrane, the COF-Me membrane immersed in organic solvents, and the re-dried COF-Me membrane. These data were collected using a Bruker D8 Eiger system. “2θ” is the angle between the incident X-ray beam and the diffracted X-ray beam, with the unit of degree. The columns labeled “COF-Me membrane (Dry)”, “COF-Me (Wet)”, and “COF-Me (Redry)” indicate the XRD intensities of the dry, wet, and re-dried COF-Me membranes, respectively.
File: Fig_S28.xlsx
Description: This file contains the XRD profiles for Fig. S28 in the supplementary materials. The data show the XRD patterns of the pristine dry COF-Hex membrane, the COF-Hex membrane immersed in organic solvents, and the re-dried COF-Hex membrane. These data were collected using a Bruker D8 Eiger system. “2θ” is the angle between the incident X-ray beam and the diffracted X-ray beam, with the unit of degree. The columns labeled “COF-Hex membrane (Dry)”, “COF-Hex (Wet)”, and “COF-Hex (Redry)” indicate the XRD intensities of the dry, wet, and re-dried COF-Hex membranes, respectively.
File: Fig_S44.xlsx
Description: This file contains the FT-ICR MS data for Fig. S44 in the supplementary materials. The data show Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) spectra of the feed, fraction 1, and fraction 2. The data were collected using a SolariX XR ultra-high-resolution FT-ICR MS instrument (Bruker Daltonik GmbH, Bremen, Germany) equipped with a 9.4 T refrigerated superconducting cryomagnet. “m/z” refers to the mass-to-charge ratio of detected ions, with the unit of m/z. “Intensity” refers to the signal strength of ions detected at a given m/z, reflecting the relative abundance of ions at that m/z, with the unit of a.u. “Intensity” in columns B, D, and F indicates the intensity of the feed, fraction 1, and fraction 2, respectively.
File: Fig_S47.xlsx
Description: This file contains the XRD profile for Fig. S47 in the supplementary materials. The data show the XRD pattern of the COF-But membrane after two months of continuous operation with real crude oil. The data were collected using a Bruker D8 Eiger system. “2θ” is the angle between the incident X-ray beam and the diffracted X-ray beam, with the unit of degree. “Intensity” refers to the strength of the diffracted X-ray signal detected at a given 2θ angle, with the unit of a.u.
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