WO2021154150A1 - Method for producing a film of a 3d porous aromatic framework - Google Patents
Method for producing a film of a 3d porous aromatic framework Download PDFInfo
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- WO2021154150A1 WO2021154150A1 PCT/SE2021/050065 SE2021050065W WO2021154150A1 WO 2021154150 A1 WO2021154150 A1 WO 2021154150A1 SE 2021050065 W SE2021050065 W SE 2021050065W WO 2021154150 A1 WO2021154150 A1 WO 2021154150A1
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- 239000013312 porous aromatic framework Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 238000005859 coupling reaction Methods 0.000 claims abstract description 12
- 230000008878 coupling Effects 0.000 claims abstract description 11
- 238000010168 coupling process Methods 0.000 claims abstract description 11
- 239000013476 3D covalent-organic framework Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000003380 quartz crystal microbalance Methods 0.000 claims description 23
- 239000010931 gold Substances 0.000 claims description 21
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052737 gold Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 10
- YBGIIZGNEOJSRF-UHFFFAOYSA-N 1-bromo-4-[tris(4-bromophenyl)methyl]benzene Chemical compound C1=CC(Br)=CC=C1C(C=1C=CC(Br)=CC=1)(C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 YBGIIZGNEOJSRF-UHFFFAOYSA-N 0.000 claims description 9
- 238000004626 scanning electron microscopy Methods 0.000 claims description 9
- 238000012544 monitoring process Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003384 imaging method Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 112
- 229910052799 carbon Inorganic materials 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000013310 covalent-organic framework Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002094 self assembled monolayer Substances 0.000 description 8
- 239000013545 self-assembled monolayer Substances 0.000 description 8
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000004630 atomic force microscopy Methods 0.000 description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
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- 230000003746 surface roughness Effects 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000010453 quartz Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000013473 2D covalent-organic framework Substances 0.000 description 1
- FTBCOQFMQSTCQQ-UHFFFAOYSA-N 4-bromobenzenethiol Chemical compound SC1=CC=C(Br)C=C1 FTBCOQFMQSTCQQ-UHFFFAOYSA-N 0.000 description 1
- 241000819038 Chichester Species 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 150000002466 imines Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/40—Details relating to membrane preparation in-situ membrane formation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/13—Morphological aspects
- C08G2261/135—Cross-linked structures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3424—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms non-conjugated, e.g. paracyclophanes or xylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/412—Yamamoto reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/94—Applications in sensors, e.g. biosensors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Definitions
- the disclosure relates to a method for producing a film of a 3D porous aromatic framework, or a film of a 3D covalent organic framework, in accordance with the preamble of appended claim 1.
- the disclosure also relates to a film being produced by means of said method, in accordance with the preamble of appended claim 12.
- Covalent organic frameworks were first synthesized by Yaghi and coworkers in 2005 and represent a class of porous, structurally regular materials that contain only light elements (i.e., B, C, N, H, and O).
- 1 Organic framework materials have a unique suite of properties such as ultrahigh thermal stability (up to 500 °C), 2 3 low densities (0.13 g cm -3 ), 4 and high internal surface area (7000 m 2 g -1 ). 5 This confluence of properties make this class of materials highly suitable for various applications such as chemical separations, 6 8 catalysis, 9 11 gas storage, 12 14 water purification, 15 drug delivery, 16 18 electrode materials, 19 20 and sensing.
- Porous aromatic frameworks are similar to COFs that are synthesized by irreversible cross-coupling reactions. Because these materials are unable to anneal defects, due to the irreversible nature of their chemical linkages, PAFs are frequently thought to have a disordered nanoscale structure.
- 3D three-dimensional
- organic frameworks nonplanar building blocks are covalently cross-linked in all dimensions. 2 ' 4 ⁇ 22 29 This topology leads to channels in all dimensions, with pore spaces of defined shape and size that can be chemically engineered according to a desired function.
- 11 ⁇ 3031 We find that 3D frameworks are underrepresented in the literature compared to two-dimensional (2D) variants.
- films of 3D frameworks are especially challenging to synthesize and represent a frontier in synthetic framework chemistry.
- This limited exploration is partially due to the higher difficulty in synthesizing homogenous films of 3D organic frameworks compared to 2D variants. 32
- This difficulty is accentuated when considering the synthesis of carbon-carbon linked 3D frameworks which will be unable to anneal their defects through dynamic chemistry.
- an improved method with the features as defined in appended claim 1. Accordingly, there is provided a method for producing a film of a 3D porous aromatic framework with a controlled thickness. Further, accordingly, the method is also provided for producing a film of a 3D covalent organic framework with a controlled thickness.
- the method comprises the following steps: providing a pretemplated surface as a support for producing said film; adding a relatively low steady-state concentration of monomers to said pretemplated surface; and providing a controlled growth of said film, to a controlled thickness, by means of a flow of said monomers with coupling reagents on said pretemplated surface.
- the disclosure is not limited to the use of carbon in a linked 3D porous aromatic framework.
- nitrogen, oxygen and silicon could alternatively be used.
- the method comprises the following steps: providing a pretemplated surface as a support for producing said film; adding a concentration of monomers to said pretemplated surface, wherein said concentration has been reduced below a threshold where reaction on the surface will dominate over bulk reaction; and providing a controlled growth of said film, to a controlled thickness, by means of a flow of said monomers with coupling reagents on said pretemplated surface.
- reaction parameters and conditions e.g. temperature/s, for example, reaction temperature/s
- reaction system parameters and conditions e.g. reactor parameters and conditions, for example, continuous reactor parameters and conditions
- reaction process parameters and conditions for example, continuous reaction parameters and conditions.
- the method may comprise a step of adding said monomers in a concentration with a magnitude which is chosen so that a bulk reaction during said growth is considerably reduced in comparison with the growth of said film.
- the method further may comprise a step of providing said flow as a continuous flow in which said monomers and coupling reagents are mixed immediately before a reactor which is configured for growth of said surface.
- the method may comprise a step of providing said pretemplated surface of a material which is adapted for connecting said porous aromatic framework to said surface.
- the method may comprise a step of providing said surface in the form of gold or a similar metal. This means that other metals than gold can be used in order to provide a connection between said porous aromatic framework and said surface.
- the method may comprise a step of providing said surface in the form of silicon oxide or a similar non-metal substance.
- silicon oxide or a similar non-metal substance.
- the method may comprise a step of providing said monomers in the form of tetrakis(4-bromophenyl)methane (TBPM) or structurally similar molecules, i.e. having generally the same geometry.
- TBPM tetrakis(4-bromophenyl)methane
- the method may comprise a step of monitoring the growth of said film.
- the method may comprise a step of monitoring the growth by means of a quartz crystal microbalance (QCM).
- the method may comprise a step of correlating the QCM signal by means of scanning electron microscopy (SEM) cross section imaging.
- Figure 1 shows a schematic overview of a reaction leading to a film
- Figure 2 shows optical images of porous aromatic framework films
- Figure 3 shows a process of monitoring the film growth and an example of the surface morphology of said film.
- Figure 4 shows a process of confirming an elemental composition.
- an all carbon-linked continuous 3D porous aromatic framework film with nanometer precise controllable thickness is provided.
- frameworks synthesized by homo-coupling of a single monomer species can occur between monomers and oligomers in solution or between monomers and the film surface.
- C-C bonds are robust, providing rigidity and chemical stability to the obtained structure.
- C-C cross-coupling prevent dynamic rearrangement, which prevents defects from being annealed. Once the bonds are formed, they do not break and a kinetically favored rather than the thermodynamically favored product may be trapped. Therefore, that initial formation of a structurally regular material is necessary for the synthesis of a smooth, homogenous films.
- the film must be synthesized epitaxially.
- the same reaction that leads to productive surface growth may also take place in solution, resulting in larger aggregates that can contaminate the film.
- the challenge is to restrict homogenous nucleation of framework powders while promoting uniform, layer-by-layer heterogeneous growth of framework films. 4243
- Figure 1 is a schematic overview of the reaction on the surface leading to a continuous film.
- the reaction rate between two species, whether monomers or oligomers, in solution is expected to follow second order kinetics with respect to the concentration of the monomer.
- concentration of one of the reactants the surface
- the relevant rate equations for the monomer-monomer and the monomer-surface reactions are as follows: where ris the reaction rate and k is the relevant reduced rate constant (including the concentration of non-monomeric coupling reagents, catalysts, etc.). This difference in reaction kinetics indicates that at high concentration, monomers will predominantly react to form oligomers, which at some critical size will precipitate from solution.
- PAF-1 5 ⁇ 44 (also published as PPN-6) 45 was chosen.
- PAF-1 tetrakis(4-bromophenyl)methane
- TBPM tetrakis(4-bromophenyl)methane
- Figure 2 shows optical images of PAF-1 films.
- A) Batchmode an immersed templated gold sensor in a solution of monomers and coupling reagents, leading to a macroscopic nonuniform surface.
- Figure 2 displays microscope images of films made using bulk or flow conditions. In bulk conditions, the film is very rough (Figure 2A), which is consistent with previously reported approaches. 41 We suspect that in this case, oligomers have most first formed in solution and later bind to the surface, providing macroscopic non-uniform structures. On the other hand, flow conditions produce a film that is smooth on a macroscopic level as evident from the absence of scattering in the uniform microscope image ( Figure 2B). If thiophenol instead of 4-bromothiophenol is used in the SAM layer, the ability to form covalent bonds between the SAM and the porous film is removed (Figure 2C).
- Figure 3 shows a process of monitoring the film growth.
- QCM measures the mass change as a shift of the quartz resonance frequency over time. The frequency shift correlates directly to the thickness of the film, and the slope of the frequency shift relates to the reaction rate on the film surface.
- Figure 3A displays the frequency shift as a function of reaction time.
- Figure 4 shows confirming the elemental composition.
- A-B Depth XPS spectrum, showing the existence of gold (B) right underneath the carbon (A) containing film.
- C-E EDX-SEM measurements on the cross section of a film. The elements shown in area A (blue) match the existence of a PAF-1 based film (carbon) and the gold surface on chromium (very thin adhesive layer between silicon and gold).
- Area B shows the existence of silicon (quartz crystal) and Cr.
- Figure 4a-4b shows the carbon and gold content of the film and substrate at varying etching times. At short distance into the film, only carbon signal was observed consistent with signal from PAF-1. In contrast, deeper in the sample the carbon signal vanished and the signal from the gold substrate concurrently appeared. This XPS analysis is consistent with our understanding of a fully carbon-hydrogen framework adhered to the gold substrate.
- the element composition was also explored on a film cross section ( Figure 4B-C) using EDX-SEM. By targeting the film on the sensor surface (bright gray in B), the main elements found were gold, chromium, and carbon.
- the gold signal arises from the roughly 100-nm thick gold coating on the sensor and chromium is used as an adhesive layer between gold and the silicon crystal.
- the carbon signal originates from the deposited film. Measuring further away from the PAF-1 film, deeper into the sensor, only silicon and chromium gave prominent signals.
- the measured element composition matched the information given by the manufacturer (Biolin Scientific), further confirming the expected element composition of the PAF film (see Figures S3-4 for additional SEM images and EDX spectra).
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- Health & Medical Sciences (AREA)
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Abstract
The present disclosure relates to a method for producing a film of a 3D porous aromatic framework, or a film of a 3D covalent organic framework, with a controlled thickness, said method process comprising the following steps: providing a pretemplated surface as a 5 support for producing said film; adding a relatively low steady-state concentration of monomers to said pretemplated surface; and providing a controlled growth of said film, to a controlled thickness, by means of a flow of said monomers with coupling reagents on said pretemplated surface; and a film being produced by means of the method.
Description
METHOD FOR PRODUCING A FILM OF A 3D POROUS AROMATIC FRAMEWORK TECHNICAL FIELD
The disclosure relates to a method for producing a film of a 3D porous aromatic framework, or a film of a 3D covalent organic framework, in accordance with the preamble of appended claim 1.
The disclosure also relates to a film being produced by means of said method, in accordance with the preamble of appended claim 12. BACKGROUND
Inherently porous materials that are chemically and structurally robust are challenging to construct. Conventionally, dynamic chemistry is thought to be needed for the formation of uniform porous organic frameworks, but dynamic bonds can limit the stability of these materials. For this reason, all carbon linked frameworks are expected to exhibit higher stability performance than more traditional porous frameworks. However, the limited reversibility of carbon-carbon bond forming reactions has restricted the exploration of these materials. In particular, the challenges associated with producing uniform thin films of all carbon-linked frameworks has reduced the ability to study these materials in applications where well-defined films are required.
Covalent organic frameworks (COFs) were first synthesized by Yaghi and coworkers in 2005 and represent a class of porous, structurally regular materials that contain only light elements (i.e., B, C, N, H, and O).1 Organic framework materials have a unique suite of properties such as ultrahigh thermal stability (up to 500 °C),2 3 low densities (0.13 g cm-3),4 and high internal surface area (7000 m2 g-1).5 This confluence of properties make this class of materials highly suitable for various applications such as chemical separations,6 8 catalysis,9 11 gas storage,12 14 water purification,15 drug delivery,16 18 electrode materials,19 20 and sensing.21 Porous aromatic frameworks (PAFs) are similar to COFs that are synthesized by irreversible cross-coupling reactions. Because these materials are unable to anneal defects, due to the irreversible nature of their chemical linkages, PAFs are frequently thought to have a disordered nanoscale structure. In three-dimensional (3D) organic frameworks nonplanar building blocks are covalently cross-linked in all dimensions.2'4·22 29 This topology leads to channels in all dimensions, with pore spaces of defined shape and size that can be chemically engineered according to a desired
function.11·3031 We find that 3D frameworks are underrepresented in the literature compared to two-dimensional (2D) variants. In particular, films of 3D frameworks are especially challenging to synthesize and represent a frontier in synthetic framework chemistry. This limited exploration is partially due to the higher difficulty in synthesizing homogenous films of 3D organic frameworks compared to 2D variants.32 This difficulty is accentuated when considering the synthesis of carbon-carbon linked 3D frameworks which will be unable to anneal their defects through dynamic chemistry.
Although 3D COFs and 3D PAFs have been synthesized as microcrystalline powders, many promising applications (e.g. membranes or electronics) for these materials will require films.33 This understanding has inspired immense interest in synthesizing COFs and PAFs as uniform films, which can be more readily interfaced with these applications. Recently, films of 2D frameworks have been made on templated surfaces using batch solvothermal conditions.3435 Other strategies for the synthesis of uniform 2D films include exfoliation and reassembly,36 interfacial crystallization of thin 2D films at liquid-liquid 37 or air-liquid interfaces,38 and blade-casting of precursors.6 Expanding on these batch reaction approaches, Bisbey and coworkers used a continuous flow set-up in combination with a quartz crystal microbalance to measure the deposited mass of a 2D COF on a Ti surface in real time, giving control of the film thickness.39 However, topological differences between 2D and 3D frameworks mean that methods used to construct 2D based films cannot be readily adapted for 3D framework film synthesis. Films of 3D COFs have been made using dynamic imine or boronate ester bonds.40 However, to date, the only example of an all carbon-linked 3D framework was described by Becker and coworkers in 2015; were they used a templated surface and batch conditions to form a 3D PAF-1 film with micron scale roughness.41 Although this report shows that carbon-carbon bonded 3D frameworks can be obtained as films, they showed unwieldy surface roughness, powder contamination, and unpredictable thickness. However, this preliminary report led us to speculate that the synthesis of smooth 3D framework films with precise thickness based on carbon-carbon bonds is now within reach, a crucial step towards maximizing the utility of this class of promising materials.
SUMMARY
In accordance with the disclosure, there is provided an improved method with the features as defined in appended claim 1. Accordingly, there is provided a method for producing a film of a 3D porous aromatic framework with a controlled thickness. Further, accordingly,
the method is also provided for producing a film of a 3D covalent organic framework with a controlled thickness.
The method comprises the following steps: providing a pretemplated surface as a support for producing said film; adding a relatively low steady-state concentration of monomers to said pretemplated surface; and providing a controlled growth of said film, to a controlled thickness, by means of a flow of said monomers with coupling reagents on said pretemplated surface.
Here, and in accordance with different embodiments, we synthesize continuous and homogenous films of an all carbon linked 3D porous aromatic framework (PAF-1) with nanometer precision thickness. This is accomplished by kinetically promoting surface reactivity while suppressing homogenous nucleation. By connecting the PAF film to a gold substrate via a self-assembled monolayer and using flow conditions to continually introduce monomers, smooth and continuous PAF films can be grown with controlled thickness. This strategy allows traditional transition metal-mediated carbon-carbon cross coupling reactions to form porous, organic thin films. We expect that the chemical principles uncovered in this study will enable the synthesis of a variety of chemically and structurally diverse carbon-carbon linked frameworks as high-quality films, which are inaccessible by conventional methods.
The disclosure is not limited to the use of carbon in a linked 3D porous aromatic framework. As examples, nitrogen, oxygen and silicon could alternatively be used.
Further, the method, as described herein, comprises the following steps: providing a pretemplated surface as a support for producing said film; adding a concentration of monomers to said pretemplated surface, wherein said concentration has been reduced below a threshold where reaction on the surface will dominate over bulk reaction; and providing a controlled growth of said film, to a controlled thickness, by means of a flow of said monomers with coupling reagents on said pretemplated surface.
The specific “relatively low steady-state concentration” and the specific “concentration wherein said concentration has been reduced below a threshold where reaction on the surface will dominate over bulk reaction”, as described herein, are dependent on various parameters and conditions, such as, reaction parameters and conditions, e.g. temperature/s, for example, reaction temperature/s; reaction system parameters and
conditions, e.g. reactor parameters and conditions, for example, continuous reactor parameters and conditions; and reaction process parameters and conditions, for example, continuous reaction parameters and conditions.
According to an embodiment, the method may comprise a step of adding said monomers in a concentration with a magnitude which is chosen so that a bulk reaction during said growth is considerably reduced in comparison with the growth of said film.
According to an embodiment the method further may comprise a step of providing said flow as a continuous flow in which said monomers and coupling reagents are mixed immediately before a reactor which is configured for growth of said surface.
According to an embodiment, the method may comprise a step of providing said pretemplated surface of a material which is adapted for connecting said porous aromatic framework to said surface.
According to an embodiment, the method may comprise a step of providing said surface in the form of gold or a similar metal. This means that other metals than gold can be used in order to provide a connection between said porous aromatic framework and said surface.
According to an embodiment, the method may comprise a step of providing said surface in the form of silicon oxide or a similar non-metal substance. This means that other non- metal substances than silicon oxide can be used in order to provide a connection between said porous aromatic framework and said surface.
According to an embodiment, the method may comprise a step of providing said monomers in the form of tetrakis(4-bromophenyl)methane (TBPM) or structurally similar molecules, i.e. having generally the same geometry.
According to an embodiment, the method may comprise a step of monitoring the growth of said film.
According to an embodiment, the method may comprise a step of monitoring the growth by means of a quartz crystal microbalance (QCM).
According to an embodiment, the method may comprise a step of correlating the QCM signal by means of scanning electron microscopy (SEM) cross section imaging.
According to the disclosure, there is also provided a film as defined in appended claim 12, i.e. as produced by means of the above-mentioned method.
BRIEF DESCRIPTION OF THE FIGURES
The process and film according to the disclosure will be described in greater detail below and with reference to the figures shown in the appended drawings.
Figure 1 shows a schematic overview of a reaction leading to a film;
Figure 2 shows optical images of porous aromatic framework films;
Figure 3 shows a process of monitoring the film growth and an example of the surface morphology of said film; and
Figure 4 shows a process of confirming an elemental composition. DETAILED DESCRIPTION
Different aspects of the present disclosure will be described more fully hereinafter with reference to the enclosed drawings. The disclosure can be realized in many different forms and should not be construed as being limited to the embodiments below. According to an embodiment of the disclosure, there is provided an all carbon-linked continuous 3D porous aromatic framework film with nanometer precise controllable thickness.
Here, we show for the first time that it is possible to construct all carbon-linked 3D PAFs as smooth and continuous films with controllable thicknesses. This new synthesis method works by introducing monomers at low steady-state concentrations in flow to a pretemplated substrate. This approach favors film growth over bulk powder synthesis, which can contaminate the desired films. A quartz crystal microbalance (QCM) was used to monitor the growth of the film in real time and scanning electron microscopy (SEM) cross section imaging was used to correlate the QCM signal to film thickness, allowing for nanometer thickness control. Continuous flow conditions constantly remove in bulk
formed oligomers, resulting in an improved smoothness of the obtained film by limiting the precipitation of bulk framework materials. Films were further characterized via depth dependent X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy - scanning electron microscopy (EDX-SEM), which show that the desired C- C polymerization chemistry had taken place. Furthermore, surface roughness was probed by atomic force microscopy (AFM) which demonstrated that the films were smooth, continuous, and free from powder contamination. This work provides a strategy to overcome the former restrictions of 3D film synthesis that we suspect will enable the construction of a broad range of porous materials in a useful configuration for a host of applications.
RESULTS AND DISCUSSION
To construct a film of framework material, it is crucial to spatially control polymerization. For example, frameworks synthesized by homo-coupling of a single monomer species can occur between monomers and oligomers in solution or between monomers and the film surface. C-C bonds are robust, providing rigidity and chemical stability to the obtained structure. However, C-C cross-coupling prevent dynamic rearrangement, which prevents defects from being annealed. Once the bonds are formed, they do not break and a kinetically favored rather than the thermodynamically favored product may be trapped. Therefore, that initial formation of a structurally regular material is necessary for the synthesis of a smooth, homogenous films. Additionally, if precise thicknesses, low roughness films are to be obtained, the film must be synthesized epitaxially. However, the same reaction that leads to productive surface growth may also take place in solution, resulting in larger aggregates that can contaminate the film. Stated another way, the challenge is to restrict homogenous nucleation of framework powders while promoting uniform, layer-by-layer heterogeneous growth of framework films.4243
Figure 1 is a schematic overview of the reaction on the surface leading to a continuous film. A) The building block, tetrakis(4-bromophenyl)methane (TBPM). B) The self assembled monolayer (SAM) formation on the gold QCM chips. C) A continuous flow set up with three autonomous programmable syringe pumps pushing the fluids through the QCM chamber where the reaction on the surface takes place, forming the COF film.
The reaction rate between two species, whether monomers or oligomers, in solution is expected to follow second order kinetics with respect to the concentration of the monomer. In contrast, when monomer couples to the surface, the concentration of one of
the reactants (the surface) is fixed and so pseudo-first order kinetics would be expected. Thus, the relevant rate equations for the monomer-monomer and the monomer-surface reactions are as follows:
where ris the reaction rate and k is the relevant reduced rate constant (including the concentration of non-monomeric coupling reagents, catalysts, etc.). This difference in reaction kinetics indicates that at high concentration, monomers will predominantly react to form oligomers, which at some critical size will precipitate from solution. When reducing the concentration, the bulk reaction will be reduced in comparison to surface growth. Therefore, below a certain concentration threshold, the reaction on the surface will dominate, which we hypothesize would be ideal for the synthesis of uniform C-C linked framework films. To show that it is possible to synthesize a continues framework film, the well-known PAF system PAF-15·44 (also published as PPN-6)45 was chosen. In PAF-1, tetrakis(4-bromophenyl)methane (TBPM; Figure 1) is used as a building block, which forms a 3D network via Yamamoto coupling.46 PAF-1 has an exceptionally high surface area and excellent hydrothermal stability due to the chemical stability of the C-C bond and its powders have found use in gas storage applications.5
Figure 2 shows optical images of PAF-1 films. A) Batchmode: an immersed templated gold sensor in a solution of monomers and coupling reagents, leading to a macroscopic nonuniform surface. B) Continuous flow: Mixing of monomers and coupling reagents just before the flow reactor leads to a continuous and smooth film. C) Continuous flow: Numerous cracks are evident when using a non-brominated SAM under the same reaction conditions. D) Continuous flow: Cracks and powder contamination are also present when using a ten-fold higher concentration than those used in B.
When making a film via a bottom-up approach, adhesion between the substrate and the first layer of the framework film is necessary. Because thiols are known to diffuse laterally on Au surfaces, giving the possibility for structures attached by such bonds to self- organize, we selected a thiol functionalization strategy to create a well adhered first layer of the film. To achieve this, a gold-coated QCM wafer was exposed to 4- bromothiophenole, which forms a self-assembled monolayer on the gold surface (Figure 1).41 This molecule is bromine-functionalized at the para position, allowing for Yamamoto coupling reaction with the PAF-1 monomer (TBPM). We expect that a fully thiol
functionalized SAM will react with the appropriate number of TBPMs to yield a monolayer that will serve as a template for PAF formation. Previously, researchers have used a thiol- templated surface to connect PAF-1 to a surface.41 We have extended this strategy to yield continuous 3D PAF films by (1) limiting the steady state concentration of monomer, about 1% of the concentration previously demonstrated to synthesize PAF-1,41 and (2) using continuous flow conditions that provide clean reagents throughout the reaction and limits powder aggregation. To accommodate these adaptations, we built a continuous flow cell set-up based on three programmable syringe pumps, a mixing unit, and a quartz crystal microbalance (QCM) flow cell (Figure 1). The monomer and coupling reagents were kept in separate syringes and mixed just before entering the QCM flow cell. Figure 2 displays microscope images of films made using bulk or flow conditions. In bulk conditions, the film is very rough (Figure 2A), which is consistent with previously reported approaches.41 We suspect that in this case, oligomers have most first formed in solution and later bind to the surface, providing macroscopic non-uniform structures. On the other hand, flow conditions produce a film that is smooth on a macroscopic level as evident from the absence of scattering in the uniform microscope image (Figure 2B). If thiophenol instead of 4-bromothiophenol is used in the SAM layer, the ability to form covalent bonds between the SAM and the porous film is removed (Figure 2C). This results in cracks in- between relatively flat regions. The lack of connection between the surface and the framework most likely results in PAF grains first precipitating on the surface, and these grains then grow. Cracks and an uneven distribution could also be observed when using flow conditions with a 10 times higher concentration of all reagents (Figure 2D) when compared to the conditions used in Figure 2B. Furthermore, the surface roughness (as measured with AFM) increased when increasing the concentrations above a certain point (Figure S1). High concentration conditions also resulted in the formation of visible aggregates in the tubing after the mixing unit. These experiments demonstrate that surface connectivity, low concentration, and flow conditions are needed to form a uniform framework film. In the next section, we examine the build-up of the film in real time, enabling the construction of films with nanometer precision thickness.
Figure 3 shows a process of monitoring the film growth. A) Typical frequency change during the reaction. B) SEM picture with 69,000 times magnification of the film cross section, showing the existence of a smooth film. C) Plot showing a linear correlation between the frequency change and the film thickness D) AFM image of an 150 nm thick film, having a mean square roughness of 4 nm.
To monitor the buildup of the framework film in real-time, a QCM was used. QCM measures the mass change as a shift of the quartz resonance frequency over time. The frequency shift correlates directly to the thickness of the film, and the slope of the frequency shift relates to the reaction rate on the film surface. Figure 3A displays the frequency shift as a function of reaction time. A nearly linear dependence between the frequency shift versus time is evident, indicating that the rate of reaction on the surface is constant when monomer concentration is held constant as indicated by equation 2. However, when reducing the flow speed under the same concentration, a lower slope in the frequency shift over time was observed (Figure S2). The boundary layer is the area of the fluid close to the solid surface (in our case the surface of the film). The velocity of the fluid in the boundary layer decreases towards zero when approaching the surface. The only possibility for building blocks to reach the surface is therefore via diffusion through this layer. The thickness of the boundary layer is flow speed dependent. When reducing the flow speed, the thickness of the boundary layer increases, which causes a reduction in the growth rate.47 This observation suggests that the reaction rate on the surface is limited by mass transport close to the surface, which is affected by the flow speed. Furthermore, SEM showed a completely flat film within the spatial resolution of the instrument (Figure 3B, Figures S3-S4), and AFM showed a mean roughness of less than 4 nm over an area of 4 pm2 (Figure 3D). The formed films can therefore be regarded as homogenous on the macroscopic scale and smooth on the nano scale.
In order to correlate the frequency shift to film thickness, QCM chips were broken and cross section imaging was performed via SEM (Figure 3B). Figure 3C displays a linear relation between film thickness (as measured with SEM) and frequency shift (measured with QCM), indicating that the mass density profile of the film is homogenous. This finding allowed us to calculate the frequency to thickness relationship to 0.057 nm Hz 1. We considered the possibility that encaged solvent molecules might influence the frequency shift and thus the measured mass. To see whether solvent contributes to the frequency shift, we compared the change in frequency shift of a film and a clean gold surface when changing the solvent from tetrahydrofuran (THF) to deuterated THF (Figure S5). We observed a difference between the two substrates, indicating that caged solvent molecules do influence the measured weight. Thus, the observed frequency shift originates not only from the film but also from caged solvent molecules. Furthermore, the constant relating frequency shift to film thickness is therefore dependent on the solvent used. Interested to evaluate the porous structure of our PAF-1 films, we evaluated the electron density with X-ray reflectivity measurements. We find that the electron density is
approximately -0.6 e A'3 (Figure S7). While this is nearly double an idealized structure, we expect that structural defects, framework intercalation, residual solvent, and catalyst would all lead to more dense structures than that of the ideal PAF-1. Importantly, similarly dense PAF-1 materials have also been found to have exceptional surface areas.48 This finding is consistent with the understanding that solvent molecules are intercalated into the framework (Figure S5), giving rise to solvent dependent shifts of the observed QCM frequency. Thus, by controlling the introduction of monomers to a pretemplated surface, it is possible to create smooth, porous 3D framework films with controllable thickness.
Figure 4 shows confirming the elemental composition. A-B) Depth XPS spectrum, showing the existence of gold (B) right underneath the carbon (A) containing film. C-E) EDX-SEM measurements on the cross section of a film. The elements shown in area A (blue) match the existence of a PAF-1 based film (carbon) and the gold surface on chromium (very thin adhesive layer between silicon and gold). Area B (red) shows the existence of silicon (quartz crystal) and Cr.
To examine the chemical composition of the formed film on top of a gold substrate, we measured the XPS signal as a function of etching time. Figure 4a-4b shows the carbon and gold content of the film and substrate at varying etching times. At short distance into the film, only carbon signal was observed consistent with signal from PAF-1. In contrast, deeper in the sample the carbon signal vanished and the signal from the gold substrate concurrently appeared. This XPS analysis is consistent with our understanding of a fully carbon-hydrogen framework adhered to the gold substrate. The element composition was also explored on a film cross section (Figure 4B-C) using EDX-SEM. By targeting the film on the sensor surface (bright gray in B), the main elements found were gold, chromium, and carbon. The gold signal arises from the roughly 100-nm thick gold coating on the sensor and chromium is used as an adhesive layer between gold and the silicon crystal. The carbon signal originates from the deposited film. Measuring further away from the PAF-1 film, deeper into the sensor, only silicon and chromium gave prominent signals. The measured element composition matched the information given by the manufacturer (Biolin Scientific), further confirming the expected element composition of the PAF film (see Figures S3-4 for additional SEM images and EDX spectra).
CONCLUSION
We have successfully constructed a continuous and smooth film of a 3D porous aromatic framework (PAF-1) with nanometer precise controllable thickness. QCM was used to
provide real time monitoring of the film growth and cross section SEM was used to correlate the QCM signal to film thickness. This was realized by continually introducing a sufficiently low steady-state concentration of monomers to a pretemplated surface. The approach is based on fundamental chemical principles, and we therefore believe it will enable the synthesis of a variety of 3D carbon-linked framework materials as uniform films. Furthermore, we envision that the modular flow approach described here can be used to make heterostructured framework films. We suspect that by flowing different monomers in series, diverse framework materials can be assembled sequentially within a continuous film. This approach of making 3D framework films opens up this class of material to applications where robustly adhered films of all carbon-linked porous material is required.
The method for producing a film, as described herein, as well as the embodiments, the disclosures, the aspects and the examples, also as described herein, all also apply, mutatis mutandis, to 3D covalent organic frameworks, and to films of 3D covalent organic framework produced by means of said method for producing a film, as described herein.
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Claims
1. A method for producing a film of a 3D porous aromatic framework, or a film of a 3D covalent organic framework, with a controlled thickness, said method comprising the following steps:
- providing a pretemplated surface as a support for producing said film;
- adding a relatively low steady-state concentration of monomers to said pretemplated surface; and
- providing a controlled growth of said film, to a controlled thickness, by means of a flow of said monomers with coupling reagents on said pretemplated surface.
2. A method according to claim 1, wherein said adding a relatively low steady-state concentration of monomers to said pretemplated surface, is adding a concentration of monomers to said pretemplated surface, wherein said concentration has been reduced below a threshold where reaction on the surface will dominate over bulk reaction.
3. A method according to claim 1 or 2, wherein said method further comprises:
- adding said monomers in a concentration with a magnitude which is chosen so that a bulk reaction during said growth is considerably reduced in comparison with the growth of said film.
4. A method according to anyone of claims 1 to 3, where said method further comprises:
- providing said flow as a continuous flow in which said monomers and coupling reagents are mixed immediately before a reactor which is configured for growth of said surface.
5. A method according to anyone of claims 1 to 3, wherein said method further comprises:
- providing said pretemplated surface of a material which is adapted for connecting said porous aromatic framework to said surface.
6. A method according to claim 5, wherein said method further comprises:
- providing said surface in the form of gold or a similar metal.
7. A method according to claim 5, wherein said method further comprises:
- providing said surface in the form of silicon oxide or a similar non-metal substance.
8. A method according to any one of the preceding claims, wherein said method further comprises:
- providing said monomers in the form of tetrakis(4-bromophenyl)methane (TBPM).
9. A method according to any one of the preceding claims, wherein said method further comprises:
- monitoring the growth of said film.
10. A method according to claim 9, wherein said method further comprises:
- monitoring the growth by means of a quartz crystal microbalance (QCM).
11. A method according to claim 10, wherein said method further comprises:
- correlating the QCM signal by means of scanning electron microscopy (SEM) cross section imaging.
12. A film as produced by means of the method according to any one of claims 1-11.
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