WO2017031062A1 - Conducting-polymer modified covalent organic frameworks and methods of making same - Google Patents

Abstract

Provided are covalent organic framework layers with conducting polymer, at least partially, disposed in the pores and/or surface of the covalent organic framework layers. Covalent organic framework layers with conducting polymer can be made by electropolymerization of one or more conducting monomers in the presence of one or more COF layers. An electronic device, such as, for example, a battery or capacitor can comprise one or more covalent organic framework layers with conducting polymer.

Description

CONDUCTING-POLYMER MODIFIED COVALENT ORGANIC FRAMEWORKS

AND METHODS OF MAKING SAME

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No.

62/205,228, filed on August 14, 2015, the disclosure of which is hereby incorporated by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0002] This invention was made with government support under DGE-1144153 awarded by the National Science Foundation and DE-FG02-87ER45298 awarded by the Department of Energy. The government has certain rights in the invention.

FIELD OF THE DISCLOSURE

[0003] The disclosure generally relates to conducting-polymer modified covalent organic frameworks. BACKGROUND OF THE DISCLOSURE

[0004] Electrical energy storage (EES) technologies that offer both high power and energy densities have motivated interest in redox-active materials for electrochemical supercapacitors. Supercapacitors store electricity through two distinct processes: the non- faradaic processes associated with the electrochemical double layer and faradaic processes arising from electrode-bound reversible redox processes, a phenomenon known as pseudocapacitance. The electrochemical double layer consists of ions adsorbed to an electrode surface in response to an applied potential and is maximized in high surface area electrodes, such as porous carbons. Redox-active groups may be covalently attached or adsorbed onto these electrodes. However, these materials are typically not well defined, which complicates their characterization and rational efforts to improve their performance. Modular and reliable strategies to access high-surface-area electrodes with control over their porosity and surface area, as well as the placement and identity of redox-active groups are desirable.

[0005] Two-dimensional covalent organic frameworks (2D COFs) predictably organize redox-active groups into crystalline, high-surface area polymer networks with uniform micropores. Electrodes functionalized with 2D COFs might achieve both high theoretical energy density by exhibiting high capacity and high potentials, and high power density because their continuous, ordered pores facilitate ion transport. Many early 2D COFs featured boron-containing linkages, which are oxidatively and hydrolytically unstable, limiting their utility as electrode materials; especially at high potentials. However, a new class of COFs linked by β-ketoenamines offers superior stability to H2O, aqueous acid, and high applied potentials, β-ketoenamine-linked COFs have served as supports for transition metal catalysts and shown promising proton conductivity.

[0006] The low conductivity of two-dimensional covalent organic frameworks (2D

COFs), and most related coordination polymers, limits their applicability in optoelectronic and electrical energy storage (EES) devices. Although some networks exhibit promising conductivity, these examples generally lack structural versatility, one of the most attractive features of framework materials design.

[0007] High surface area electrodes will provide sensing platforms, electrocatalyst supports, and improved energy storage and conversion devices, including batteries, supercapacitors, and fuel cells. In contrast to many previous strategies for accessing meso- and microporous electrodes, framework materials, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), offer uniform nanometer-scale pores and predictive design criteria to organize functional building blocks. COFs, which are crystalline polymer networks comprised of light elements, adopt two-dimensional (2D) layered structures with high spectroscopic charge-carrier mobilities. However, characterizing these properties electrochemically or utilizing COFs in electrochemical devices has been hampered by the poor hydrolytic and oxidative stability of boronate ester-linked frameworks that dominated the early COF literature.

[0008] Pseudocapacitors can combine the high energy density of batteries and superior power densities of double-layer capacitors by storing electricity through both the non-faradaic formation of an electrochemical double layer (EDL) and reversible faradaic redox processes of surface bound/immobilized species. Nanoporous electrodes, often carbon- based materials, feature high specific surface areas that maximize electrochemical double- layer formation. Although redox-active groups have been covalently bonded or adsorbed to these electrodes, their performance is often compromised by charge transfer and counter ion transport limitations. In addition, their poorly defined structures complicate characterization and rational improvement. 2D COFs address these limitations by predictably and deliberately organizing redox-active groups into insoluble, high-surface area polymer networks with uniform micropores. However, the modest conductivity of existing 2D COFs has limited devices to thin films of the active material (50-250 nm) grown on Au or carbon nanotube electrodes that only operate at slow charge/discharge rates, limiting high power performance.

SUMMARY OF THE DISCLOSURE

[0009] The present disclosure provides conducting-polymer modified covalent organic frameworks (COFs), methods of making conducting-polymer modified covalent organic frameworks, and uses thereof. The present disclosure also provides materials and devices comprising conducting-polymer modified covalent organic frameworks. Such frameworks provide materials which have properties that make them useful for applications such as, for example, incorporation in electronic devices.

[0010] In an aspect, the present disclosure provides conducting-polymer modified covalent organic frameworks. The conducting-polymer modified COFs comprise one or more COF layers and one or more conducting polymers. The conducting polymers at least partially fill a portion of or all of the COF pores and/or at least partially coat the exposed surfaces of the COFs (e.g., COF layers or COF films). The COFs are redox active COFs.

[0011] In an aspect, the present disclosure provides compositions comprising one or more conducting polymer modified COFs. For example, a thin film comprises one or more conducting polymer modified COFs (e.g., one or more conducting polymer modified COF layers).

[0012] In an aspect, the present disclosure provides a method for making conducting- polymer modified COFs as described herein. In an embodiment, the method comprises electropolymerizing a conducting-polymer in the presence of a COF (e.g., COF layer or COF layers) such that a conducting-polymer modified COF layer or layers are formed. For example, the method comprises multiple electropolymerization steps (e.g., two to 20 electropolymerization steps, including all integer number of electropolymerization steps and ranges therebetween). In an embodiment the method comprises electropolymerizing a conducting-polymer onto a COF-modified substrate.

[0013] In an aspect, the present disclosure provides devices comprising at least one conducting polymer modified COF of the present disclosure. The conducting polymer modified COFs can be incorporated in electrical devices such as, for example, electrical energy storage systems (e.g., in an electrical energy storage device such as a super capacitor). For example, an electrochemical supercapacitor comprises a conducting polymer modified COF of the present disclosure. BRIEF DESCRIPTION OF THE FIGURES

[0014] For a fuller understanding of the nature and objects of the disclosure, reference should be made to the following detailed description taken in conjunction with the accompanying figures.

[0015] Figure 1 shows the reaction scheme of the DAAQ-TFP COF film synthesis followed by electropolymerization of 3,4-ethylenedioxythiophene (EDOT) at 20 mV s^"1 in 0.1 M EDOT / 0.1 M Bu₄NC10₄.

[0016] Figure 2 shows characterization of PEDOT / DAAQ-TFP COF

nanocomposite. (A) eQCM data showing separate polymerization cycles (1^st, 2^nd, 3^rd, 4^th, and 5^th) showing a consistent uptake of 30 μg cm^"2 except for the first cycle which shows an increase of 15 μg cm^-2. (B) FTIR spectra of DAAQ-TFP COF film, 2 cycle PEDOT polymerization, 9 cycle PEDOT polymerization, and PEDOT. (C) GIXD of various polymerized DAAQ-TFP COF films. (D) XPS depth profile using an Ar ion beam etch.

[0017] Figure 3 shows (A) CV response in 0.5 M H₂S0₄ of a PEDOT modified 1 μιη DAAQ-TFP COF film and the same DAAQ-TFP COF film before EDOT polymerization (B) Oxidative charge from PEDOT modified DAAQ-TFP COF (top line) and unmodified DAAQ-TFP COF (bottom line) over various scan rates.

[0018] Figure 4 shows (A) average capacitances calculated from 10 cycles of galvanostatic charge-discharge experiments at various C rates (error bars show ±1 standard deviation). (B) Extended cycling of a PEDOT / DAAQ-TFP COF thin film showing stability over 2250 cycles.

[0019] Figure 5 shows incorporation of PEDOT within a DAAQ-TFP COF film. (A)

Depiction of modification of example of a DAAQ-TFP film by electropolymerization of 3,4-ethylenedioxythiophene (EDOT). Schematic depicts what can occur within one COF crystallite. (B) Schematic of the cross-section of a pore following the oxidation and reduction of the DAAQ moieties.

[0020] Figure 6 shows modification of a DAAQ-TFP film via electropolymerization of PEDOT. (A) Electrochemical QCM data showing separate polymerization cycles (1^st, 2^nd, 3rd. 4th _ancj ^th^ _sh_owmg _a consistent mass increase of 30 μg cm"² per cycle except for the first cycle (15 μg cm^"2). (B) Cyclic voltammograms at 20 mV s^"1 during EDOT

electropolymerization. Each cycle is corresponds with panel (A) (1^st, 2^nd, 3^rd, 4^th, and 5^th). (C) FTIR spectra of an example of an as-synthesized DAAQ-TFP film, the film after two electropolymerization cycles, a film after nine electropolymerization cycles, and PEDOT. (D) XPS depth profile (Ar ion beam etch) of the Ni_s and S_2p regions (1^st, 2^nd, 3^rd, 4^th, and 5^th). The Nis profiles are scaled three-fold in intensity for visual clarity.

[0021] Figure 7 shows electrochemical performance of examples of PEDOT-modified and as-synthesized DAAQ-TFP COF films. (A) CV response at 20 mV sec^"1 in 0.5 M H₂S0₄ of a PEDOT-modified DAAQ-TFP film, 1 μπι-thick and the same as-synthesized DAAQ- TFP film before EDOT polymerization. The inset presents the cyclic voltammetric response for the unmodified film using an expanded current scale. (B) The integrated charge associated with the oxidative wave of a PEDOT-modified DAAQ-TFP COF film and unmodified

DAAQ-TFP COF film recorded over various scan rates indicate that the PEDOT-modified films store more charge and tolerate faster scan rates than the unmodified films.

[0022] Figure 8 shows charge storage performance and device integration of an example of a PEDOT-modified DAAQ-TFP film. (A) Average capacitances calculated from 10 cycles of galvanostatic charge-discharge experiments at various C rates (error bars show ±1 standard deviation). (B) Extended cycling of a PEDOT-modified DAAQ-TFP film showing stability over 10,000 cycles. First three cycles are at a rate of IOC, then over 10,000 cycles at a rate of lOOC, followed by another three cycles at IOC showing no loss in capacitance over the cycles. (C) CV in a two-electrode device configuration, in which the counter is a high-surface area carbon electrode. (D) A potential/capacity plot obtained in a two electrode experiment exhibits well-defined voltage plateaus at the formal potential of the DAAQ moieties. (E) A PEDOT-modified DAAQ-TFP COF working device powering a green LED.

[0023] Figure 9 shows an example of a making a conducting-polymer modified covalent organic framework (COF) of the present disclosure.

[0024] Figure 10 shows representative AFMs of examples of crystalline DAAQ-TFP COF films (A) before EDOT polymerization and (B) after EDOT polymerization.

[0025] Figure 11 shows representative AFMs of examples of crystalline DAAQ-TFP

COF films (approximately 1 μπι).

[0026] Figure 12 shows representative AFM of PEDOT-modified Au AFMs for a polymerization to yield approximately 805 nm thick film for control experiments.

[0027] Figure 13 shows representative AFMs of an example of a PEDOT-modified

DAB-TFP COF film on Au.

[0028] Figure 14 shows representative SEMs of examples of post-polymerization

DAAQ-TFP COF films after polymerization for (A) 2 cycles, (B) 5 cycles, (C) 9 cycles, and (D) 18 cycles. [0029] Figure 15 shows cross sectional SEM of examples of post-polymerization

DAAQ-TFP COF film after 9 polymerization cycles.

[0030] Figure 16 shows representative GIXD of examples of DAAQ-TFP films on

Au substrates. The top row corresponds to a DAAQ-TFP COF film prior to

electropolymerization. Subsequent rows correspond to 2, 5, and 9 electropolymerization cycles, respectively.

[0031] Figure 17 shows representative GIXD of examples of DAB-TFP films on Au substrates.

[0032] Figure 18 shows GIXD of examples of PEDOT polymerized on Au substrate.

[0033] Figure 19 shows mass (left axis and left-most line) and resistance (right axis and right-most line) change for EQCM polymerization of EDOT within an example of DAAQ-TFP on QCM chip.

[0034] Figure 20 shows recorded mass (left axis and left-most line) and resistance

(right axis and right-most line) change over time with an example of EQCM

electropolymerization of EDOT on bare Au.

[0035] Figure 21 shows (A) Kr gas adsorption isotherm for a DAAQ-TFP COF without PEDOT (1), 2 cycle polymerization a PEDOT / DAAQ-TFP COF (2), and a 9 cycle polymerization PEDOT / DAAQ-TFP COF (3). BET transforms for (B) a DAAQ-TFP COF without PEDOT, (C) a 2 cycle polymerization PEDOT / DAAQ-TFP COF, and (D) a 9 cycle polymerization PEDOT / DAAQ-TFP COF.

[0036] Figure 22 shows examples of CVs used to approximate the number of anthraquinones accessed in an example of a PEDOT-modified DAAQ-TFP COF films. The left CV shows an unmodified DAAQ-TFP COF film and the right shows a PEDOT-modified DAAQ-TFP COF film

[0037] Figure 23 shows the effect of number of cycles in a EDOT polymerization on

DAAQ-TFP COF electrochemical response where lines correspond to various number of cycles in the electropolymerization as designated on the above figures. (A) Cyclic

voltammetric response of composite films in 0.5 M H2SO4, 20 mV s^"1. (B) Charge stored over a variety of scan rates.

[0038] Figure 24 shows the effect of electropolymerization scan rate. (A) Cyclic voltammograms for unmodified DAAQ-TFP COF (1) and PEDOT / DAAQ-TFP COF (2) where the PEDOT was polymerized at 2 mV s^"1 for 5 cycles. CVs taken at 20 mV s^"1 in 0.5 M H2SO4. (B) Scan rate dependence of film prepared in Figure 19 at 20 mV s^"1 (1), 50 mV s^"1 (2), and 100 mV s^"1 (3). [0039] Figure 25 shows an overlay of cyclic voltammograms (20 mV s^"1, 0.5 M

H2SO4) for a PEDOT / DAAQ-TFP COF (1), and a PEDOT / Au (2).

[0040] Figure 26 shows equivalent circuit modeling for PEDOT / DAAQ-TFP systems.

[0041] Figure 27 shows impedance spectra comparing a PEDOT / DAAQ-TFP (1) and a DAAQ-TFP COF (2).

[0042] Figure 28 shows galvanostatic charge discharge profiles over 10 cycles for a

PEDOT / DAAQ-TFP COF (A) IOC (C = cycles), (B) 20C, (C) 50C, (D) lOOC, (E) 200C, (F) 400C, (G) 800C, (H) 1600C and DAAQ-TFP COF (I) IOC, (J) 20C, (K) 50C, (L) lOOC, (M) 200C, (N) 400C, (O) 800C, (P) 1600C.

[0043] Figure 29 shows (A) Volumetric capacitances obtained from a PEDOT on gold control experiment. (B) CV of an example of PEDOT which has been

electropolymerized from EDOT on Au substrate without COF present. The CV is taken in 0.5 M H2SO4 at 20 mV s^"1. (C) Galvanostatic charge discharge profiles over 10 cycles for PEDOT / Au (D) IOC, (E) 20C, (F) 50C, (G) lOOC, (H) 200C, (I) 400C, (J) 800C.

[0044] Figure 30 shows potential / Capacity profiles for a DAAQ-TFP COF (1),

PEDOT / DAAQ-TFP COF (2), and PEDOT / Au (3).

[0045] Figure 31 shows (A) Capacitance over various C rates (x-axis) for a PEDOT /

DAAQ-TFP COF (1) over the entire voltage window (-0.4 to 0.6 V vs Ag/AgCl) and for a PEDOT / DAAQ-TFP COF (2) in the non-faradaic window (0.35 - 0.6 V V vs Ag/AgCl).

(B) CV of a PEDOT / DAAQ-TFP COF with the nonfaradaic window used in the analysis highlighted in grey. (C-J) GCDC profiles for full window (1) and nonfaradaic window (2) for a PEDOT/ DAAQ-TFP COF.

[0046] Figure 32 shows (A) Reaction scheme to synthesize an example of DAB-TFP COF film (B) CV of a PEDOT / DAB-TFP COF (1) and an unmodified DAB-TFP COF (2).

(C) Capacitance over various C rates (x-axis) for a PEDOT / DAB-TFP COF (1) a DAB- TFP COF (3) (D-K) GCDC profiles for a PEDOT / DAB-TFP COF (1) and a DAB-TFP COF (2).

[0047] Figure 33 shows galvanostatic charge / discharge experiment for an example of a PEDOT-modified DAAQ/TFP COF film at 50 C. One trace is cycle 1, the other trace is cycle 10.

[0048] Figure 34 shows extended stability test for a DAAQ-TFP COF / PEDOT after being held at -0.3 V for 15 hours using a potential step experiment. Data represents 0 h (corresponds to before potential step), 1 h, 3 h, 5 h, and 15 h. (h = hour(s)). [0049] Figure 35 shows the scan rate dependence experiment at reduced cycling rates.

(A) displays the CV response for an example of a PEDOT-modified DAAQ-TFP film at 0.5, 1, 5, and 10 mV s^"1 and (B) for 20, 50, 100, 300, and 500 mV s^"1. (C) displays the integrated charge for the oxidative and reductive anthraquinone waves along with the coulombic efficiency (CE, right y-axis) over all scan rates probed in (A) and (B). (D) is a zoom-in of the slowest scan rates shown in part (C).

[0050] Figure 36 shows capacitance responses over a variety of C-rates for a three- electrode and a two-electrode set up.

[0051] Figure 37 shows assembly of an example of a cell. Starting from the cathode, (A) Ti current collector, (B) a PEDOT / DAAQ-TFP COF, (C) separator and activated carbon, (D) Ti current collector, (E) stainless steel piece and spring, and (F) shows two cell connected in series using Arbin channels connected by wires with the LED attached to the setup.

[0052] Figure 38 shows powder XRD of an example of a PEDOT modified DAAQ- TFP powder, showing diffraction pattern maintained.

[0053] Figure 39 shows overlay of IR spectra of a DAAQ-TFP COF powder, an example of a chemically polymerized PEDOT-modified DAAQ-TFP COF powder, an example of an electropolymerized PEDOT-modified DAAQ-TFP COF film and a

electropolymerized EDOT on Au surface.

[0054] Figure 40 shows CV response for a coin cell fabricated from an example of a

PEDOT-modified DAAQ-TFP COF powder where the PEDOT to COF mass ratio is 1 : 1 (1) and similarly fabricated coin cells with only activated carbon (2) or with PEDOT only as the active material (3). The mass used in the normalization is the combined active electrode and counter electrode mass.

[0055] Figure 41 shows GCDC potential profiles for an example of a coin cell fabricated from an example of a PEDOT-modified DAAQ-TFP COF powder where the PEDOT to COF mass ration is 1 : 1 and an activated carbon counter electrode. (A)

Capacitance over a variety of C rates where the left axis is the capacitance accounting for the mass of the active electrode only and the right is the capacitance when the whole device is considered. (B) IOC (C) 20C (D) lOOC and (E) 200C.

[0056] Figure 42 shows GCDC potential profiles for an example of a coin cell fabricated from an example of a PEDOT-only coin cell with activated carbon as counter electrode. (A) Capacitance over a variety of C rates where the left axis is the capacitance accounting for the mass of the active electrode only and the right is the capacitance when the whole device is considered. (B) IOC (C) 20C (D) 50C (E) lOOC and (F) 200C.

[0057] Figure 43 shows physical mixture (grinding) of a 1-to-l PEDOT / COF mixture where the PEDOT was chemically polymerized separately from the DAAQ-TFP COF powder.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0058] Although claimed subject matter will be described in terms of certain embodiments, other embodiments, including embodiments that do not provide all of the benefits and features set forth herein, are also within the scope of this disclosure. Various structural, logical, process step, and electronic changes may be made without departing from the scope of the disclosure.

[0059] Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include all values to the magnitude of the smallest value (either lower limit value or upper limit value) and ranges between the values of the stated range.

[0060] The present disclosure provides conducting-polymer modified covalent organic frameworks (COFs), methods of making conducting-polymer modified covalent organic frameworks, and uses thereof. The present disclosure also provides materials and devices comprising conducting-polymer modified covalent organic frameworks. Such frameworks provide materials which have properties that make them useful for applications such as, for example, incorporation in electronic devices.

[0061] Conducting-polymer modified covalent organic frameworks offer a new strategy for assembling organic semiconductors into robust networks with atomic precision and long-range order. COFs incorporate organic subunits into periodic two- and three- dimensional porous crystalline structures held together by covalent bonds rather than noncovalent interactions. These linkages provide robust materials with precise and predictable control over composition, topology, and porosity. The relative geometries of the reactive groups in the starting materials determine the COF's topology, which does not change significantly as other functional groups are varied. Two-dimensional COFs can assemble functional aromatic systems into cofacially-stacked morphologies ideal for transporting excitons or charge carriers through the material. [0062] As used herein, the term "moiety", unless otherwise stated, refers to a chemical entity that has two or more termini that can be covalently bonded to other chemical species. Examples of moieties include, but are not limited to:

[0063] As used herein, the term "alkyl group", unless otherwise stated, refers to branched or unbranched hydrocarbons. Examples of such alkyl groups include substituted or unsubsituted methyl groups (-CH3), ethyl groups, propyl groups, butyl groups, isopropyl groups, tert-butyl groups, and the like. For example, the alkyl group can be a C1-C20 alkyl group including all integer numbers of carbons and ranges of numbers of carbons there between. The alkyl group can be unsubstituted or substituted with one or more substituent. Examples of substituents include, but are not limited to, various substituents such as, for example, halogens (-F, -CI, -Br, and -I), aliphatic groups (e.g., alkenes, alkynes), aryl groups, alkoxides, carboxylates, carboxylic acids, ether groups, and the like, and combinations thereof.

[0064] As used herein, the term "aryl group", unless otherwise stated, refers to a C5 to

C20 aromatic or partially aromatic carbocyclic group including all integer numbers of carbons and ranges of numbers of carbons there between. The aryl group can comprise polyaryl moieties (such as, e.g. fused rings and/or biaryl moieties). The aryl group can be

unsubstituted or substituted with one or more substituent. Examples of substituents include, but are not limited to, various substituents such as, for example, halogens (-F, -CI, -Br, and - I), aliphatic groups (e.g., alkenes, alkynes), aryl groups, alkoxides, carboxylates, carboxylic acids, ether groups, and the like, and combinations thereof. Non-limiting examples of suitable aryl groups include phenyl groups and biphenyl groups.

[0065] In an aspect, the present disclosure provides conducting-polymer modified covalent organic frameworks. The conducting-polymer modified COFs comprise one or more COF layers and one or more conducting polymers. The conducting polymers at least partially fill a portion of or all of the COF pores and/or at least partially coat the exposed surfaces of the COFs (e.g., COF layers or COF films).

[0066] The COFs are redox active COFs. The COFs are, for example, beta- ketoenamine linked COFs, imine linked COFs, hydrazone linked COFs, imide linked COFs, or boronate ester linked COFs. It is desirable that the COFs exhibit reversible redox processes. Examples of COFs and methods of making the COFs are described in Examples 1 and 2. In an embodiment, the COFs comprise co-facially stacked aromatic moieties.

Examples of suitable COFs are known in the art. Examples of suitable COFs can be made by methods known in the art.

[0067] Examples of COFs include, but are not limited to, COFs comprising redox- active 2,6-diaminoanthraquinone (DAAQ) moieties (e.g., a 2D COF linked by β- ketoenamines, imines, or enamines). The DAAQ moieties can be reduced to

9, 10-dihydroxyanthracenes upon two-electron, two-proton reduction in a protic electrolyte. For example, the COF is DAAQ-TFP COF.

[0068] The COFs can be layered sheets of 2D COFs that typically adopt nearly eclipsed stacked structures, providing continuous nanometer-scale channels normal to the stacking direction, as well as significant π-orbital overlap between monomers in adjacent layers. These features can provide an accessible high surface area interface for double-layer formation and pathways for charge transfer to/from, for example, redox-active groups that comprise the walls.

[0069] The COFs are crystalline. For example, the COFs can form crystallites (i.e., discrete structures) where the longest dimension of the crystallites can be from 50 nm to 10 microns, including all values to the nanometer and ranges of nanometers therebetween. In various embodiments, the COF comprise at least 2 unit cells, at least 5 unit cells, and at least 10 unit cells. The COFs may be present as a thin film (e.g., a film having a thickness of 10 nm to 10 microns, including all values to 10 nm and ranges therebetween).

[0070] The COF have a porous (e.g., microporous (pores with a longest dimension of less than 2 nm) or mesoporous structure (pores with a longest dimension of 2 nm to 50 nm). The porous structure forms a repeating pattern (i.e., not a random distribution of pores). In an embodiment, the framework has pores, where the pores run parallel to the stacked aromatic moieties. In an embodiment, the pores have a longest dimension (e.g., a diameter) of from 2 nm to 6 nm, including all values to the 0.05 nm and ranges to the 0.1 nm therebetween. In one example, the pores are 2.3 nm in diameter.

[0071] The COFs can have high surface area. For examples, the COFs can have a surface area 500 m²/g to 2500 m²/g, including all values to the m²/g and ranges of surface area therebetween. The surface area of the COFs can be determined by methods known in the art, for example, by BET analysis of gas (e.g., nitrogen) adsorption isotherms.

[0072] In an embodiment, one or more of the COFs have one or more redox active compounds covalently attached to the one or more of the COFs. For example, a COF comprises one or more redox active compounds or one or more moieties derived from one or more redox active compounds covalently attached to one or more moieties of the COF (e.g., one or more redox active moieties of the COF). In another example, a COF comprises one or more moieties (e.g., one or more redox active moieties of the COF) that have one or more redox active compounds or one or more moieties derived from one or more redox active compounds. In this example, the one or more redox active compounds or one or more moieties derived from one or more redox active compounds can form the sides of hexagonal repeat units of the COF.

[0073] Examples of the redox active compounds include:

In this example, n is (e.g., is independently at each occurrence in the composition) 1 to 12, alkyl is (e.g., is independently at each occurrence in the composition) a Ci to C20 alkyl group as described herein, aryl is (e.g., is independently at each occurrence in the composition) a C5 to C20 aryl group as described herein, and halogen is (e.g., is independently at each occurrence in the composition) -F, -CI, -Br, or -I.

[0074] In an embodiment, one or more conducting-polymer modified COF layers (a thin film comprising the conducting-polymer modified COF layers) are disposed on a substrate. For example, the substrate is a conducting substrate (e.g., a metal or metal coated substrate such as a gold or gold-coated substrate).

[0075] In an aspect, the present disclosure provides compositions comprising one or more conducting polymer modified COFs of the present disclosure. For example, a thin film comprises one or more conducting polymer modified COFs (e.g., one or more conducting polymer modified COF layers).

[0076] A composition can comprise one or more conducting polymer modified COFs and a carbon-containing material (e.g. a conducting carbon-containing material). Examples of carbon-containing materials include activated carbons, carbon black, graphitic carbon, graphene, carbon nanotubes, and the like. The composition can also comprise one or more binders.

[0077] In an aspect, the present disclosure provides a method for making conducting- polymer modified COFs as described herein. In an embodiment, the method comprises electropolymerizing a conducting-polymer in the presence of a COF (e.g., COF layer or COF layers) such that a conducting-polymer modified COF layer or layers are formed. For example, the method comprises multiple electropolymerization steps (e.g., two to 20 electropolymerization steps, including all integer number of electropolymerization steps and ranges therebetween). An example of a method of making conducting polymer modified COFs is shown in Figure 9.

[0078] In an embodiment the method comprises electropolymerizing a conducting- polymer onto a COF-modified substrate. The substrate can serve as a working electrode that can be used, for example, in an electropolymerization using cyclic voltammetry.

[0079] A wide variety of conducting polymers can be used in the present disclosure.

An example of a suitable conducting polymer of the present disclosure is PEDOT. Other examples of conducting polymers include poly(3,4-ethylenedioxythiophene),

poly(thiophene), poly(bithiophene), poly(pyrrole), poly(aniline), poly(acetylene),

poly(paraphenylene), poly(phenyleneethynylene), poly(benzothiophene), poly(indole), poly(3-hexylthiophene), poly(thienothiophene), poly(dithienothiophene), poly(4,4'- dimethoxybithiophene), poly(methylthiophene), poly(3-alkylthiophene), poly(n- octylthiophene), poly(fluorene), poly(carbazole), poly(N-ethylcarbazole),

poly(vinylferrocene) , poly(triphenylene), poly(azulene), poly(furan), poly(3- phenylthiophene), poly(3-[4fluorophenyl]thiophene), poly([fluoro-3-alkyl]thiophene), poly(isobenzo[c]thiophene), poly(benzothienoindole), poly(l,4-di[2-thienyl]-l,2-butadiene), poly(naphthalene), poly(anthracene), polyacene, poly(heteroacene). The conducting polymer may be amorphous.

[0080] The conducting polymers can be formed by polymerizing conducting monomers. The conducting monomers (a portion or all of the monomers) may have one or more redox active compounds covalently bonded to them.

[0081] The steps of the method described in the various embodiments and examples disclosed herein are sufficient to carry out the methods of producing conducting polymer modified COFs of the present disclosure. Thus, in an embodiment, a method consists essentially of a combination of the steps of the methods disclosed herein. In another embodiment, a method consists of such steps.

[0082] In an aspect, the present disclosure provides devices comprising at least one conducting polymer modified COF of the present disclosure. The conducting polymer modified COFs can be incorporated in electrical devices such as, for example, electrical energy storage systems (e.g., in an electrical energy storage device such as a super capacitor). For example, an electrochemical supercapacitor comprises a conducting polymer modified COF of the present disclosure.

[0083] In the following Statements, various examples of the compositions and methods of the present disclosure are described:

Statement 1. A composition comprising one or more covalent organic framework layers (COFs) of the present disclosure with conducting polymer, at least partially, disposed in the pores and/or surface of the covalent organic framework layers.

Statement 2. A composition according to Statement 1, wherein one or more of the COF layers and/or the conducting polymer comprises one or more redox active compounds and/or one or more moieties derived from redox active compounds (e.g., one or more of the COF layers (e.g., one or more of the COFs of the one or more COF layers) have one or more redox active compounds and/or one or more moieties derived from one or more redox active compound(s) covalently attached to one or more of the COF layers (e.g., one or more of the COFs of the one or more COF layers) and/or one or more of the COF layers (e.g., one or more of the COFs of the one or more COF layers) comprises one or more moieties (e.g., one or more redox active moieties of the COF(s) that comprise one or more redox active compounds and/or one or more moieties derived from one or more redox active compounds and/or the conducting polymer has one or more redox active compounds and/or one or more moieties derived from one or more redox active compounds covalently bound to the polymer).

Statement 3. A composition according to Statements 1 or 2, wherein one or more of the COF layers and/or the conducting polymer comprises at least two different redox compounds and/or one or more moieties derived from redox active compound(s).

Statement 4. A composition according to any one of the preceding Statements, where the conducting polymer is poly(3,4-ethylenedioxythiophene) PEDOT.

Statement 5. A composition according to any one of the preceding Statements, where one or more of the covalent organic framework layers comprises 2,6-diaminobenzene (DAAQ) moieties and 1,3,5-triformylphluroglucinol (TFP) moieties.

Statement 6. A composition according to any one of the preceding Statements, where one or more of the covalent organic framework layers comprises DAAQ moieties.

Statement 7. A composition according to any one of the preceding Statements, where one or more of the covalent organic framework layers comprises TFP moieties.

Statement 8. A composition according to any one of the preceding Statements, where the pores of one or more of the one or more covalent organic framework layers have a dimension of 2 mm to 50 nm.

Statement 9. A composition according to any one of the preceding Statements, where the surface area of one or more of the one or more of the covalent organic framework layers is 500 m²/g to 2500 m²/g.

Statement 10. A composition according to any one of the preceding Statements, where the composition is in the form of a thin film.

Statement 11. A composition according to Statement 10, where the thin film is disposed on at least a portion of a substrate.

Statement 12. A composition according to Statements 10 or 11, where the substrate is a metal substrate or metal-coated substrate.

Statement 13. A conducting polymer modified COF comprising a COF with conducting polymer, at least partially, disposed in the pores and/or surface of the covalent organic framework. Statement 14. A conducting polymer modified COF according to Statement 13, where the COF and/or conducting polymer comprises redox active moieties or one or more moieties derived from one or more redox active compounds (e.g., a COF has one or more redox active compounds and/or one or more moieties derived from one or more redox active compounds covalently attached to the COF and/or a COF comprises one or more moieties (e.g., one or more redox active moieties of the COF) that comprise one or more redox active compounds and/or one or more moieties derived from one or more redox active compounds and/or the conducting polymer has one or more redox active compounds and/or one or more moieties derived from one or more redox active compounds).

Statement 15. A conducting polymer modified COF according to Statements 13 or 14, where the conducting polymer comprises at least two different redox compounds and/or one or more moieties derived from redox active compound(s).

Statement 16. A conducting polymer modified COF according to any one of Statements 13 to 15, where the conducting polymer is poly(3,4-ethylenedioxythiophene) PEDOT.

Statement 17. A conducting polymer modified COF according to any one of Statements 13 to 16, where one or more of the covalent organic framework layers comprises 2,6- diaminobenzene (DAAQ) moieties and 1,3,5-triformylphluroglucinol (TFP) moieties.

Statement 18. A conducting polymer modified COF according to any one of Statements 13 to 17, where one or more of the covalent organic framework layers comprises DAAQ moieties.

Statement 19. A conducting polymer modified COF according to any one of Statements 13 to 18, wherein at least one of the covalent organic framework layers comprises TFP moieties. Statement 20. A conducting polymer modified COF according to any one of Statements 13 to 19, wherein the pores of one or more of the COF have a dimension of 2 mm to 50 nm. Statement 21. A conducting polymer modified COF according to any one of Statements 13 to 20, wherein the surface area of the COF is 500 m²/g to 2500 m²/g.

Statement 22. A conducting polymer modified COF according to any one of Statements 13 to 21, wherein the composition is in the form of a thin film.

Statement 23. A conducting polymer modified COF according to Statement 22, wherein the thin film is disposed on at least a portion of a substrate.

Statement 24. A conducting polymer modified COF according to Statements 22 or 23, wherein the substrate is a metal substrate or metal-coated substrate.

Statement 25. A method for making one or more covalent organic framework layers with conducting polymers, at least partially, disposed in the pores and/or surface of the covalent organic framework layers: electropolymerizing a conducting-monomer in the presence of one or more COF layers, wherein the one or more conducting-polymer modified COF layers are formed.

Statement 26. An electronic device comprising one or more covalent organic framework layers with conducting polymers, at least partially, disposed in the pores and/or surface of the covalent organic framework layers.

Statement 27. An electronic device according to Statement 26, wherein the device is selected from the group consisting of batteries and capacitors.

Statement 28. An electronic device according to Statements 26 or 27, wherein the capacitor is a super capacitor.

[0084] The following examples are presented to illustrate the present disclosure. They are not intended to limiting in any matter.

EXAMPLE 1

[0085] This example provides a description of methods of making and

characterization of conducting-polymer modified covalent organic frameworks of the present disclosure and films thereof. The example describes the enhanced capacitance and charging rate of conducting polymer-modified covalent organic frameworks of the present disclosure.

[0086] We describe in this example electropolymerizing 3,4-ethylenedioxythiophene

(EDOT) onto a DAAQ-TFP COF-modified working electrode, which results in the formation of poly(3,4-ethylenedioxythiophene) (PEDOT) into the pores and exposed surfaces of the COF film (Figure 1).

[0087] The resulting DAAQ-TFP COF / PEDOT composite films show more than an order of magnitude increase of charge storage capacity as compared to the unmodified

DAAQ-TFP COF films. The DAAQ-TFP COF / PEDOT composite films may also be charged and discharged much more quickly than unmodified DAAQ-TFP COF while maintaining a larger percentage of their capacity. For example, DAAQ-TFP COF / PEDOT exhibits a capacitance of 159 F cm^"3 when charged at 1600 C (2.25 s). In contrast, an unmodified DAAQ-TFP COF of the same thickness exhibits a capacitance of only 6.3 F cm^"3. The DAAQ-TFP COF / PEDOT composite films show outstanding stability to repeated charge/discharge cycles, with no loss of capacitance observed after at least 2250 cycles. These performance metrics make the DAAQ-TFP COF / PEDOT composite films competitive or superior to many established materials currently used in supercapacitors. [0088] DAAQ-TFP thin films were prepared using previously described conditions, in which a solution of TFP in DMF was added dropwise over 1 h to a solution of DAAQ in DMF containing a Au substrate. Varying the initial monomer concentration provided control of the resulting film thickness. In this example, an initial DAAQ concentration ([DAAQJo) of 22 mM provided DAAQ-TFP thin films with thicknesses of 810 ± 224 nm thick as determined by AFM. The chemical composition and crystallinity of these films were very similar to those described previously.

[0089] PEDOT was electropolymerized within a DAAQ-TFP thin film working electrode by performing cyclic voltammetry in a CFbCN solution of EDOT (100 mM, 100 mM BU4CIO4 supporting electrolyte). The voltammetric response of the system was characteristic of the electropolymerization of a conductive polymer, showing a continuous increase in current with each subsequent scan. The voltage at which these redox processes occur (-0.8 V vs Ag/AgC10₄) is also consistent with that expected for EDOT

electropolymerization. The mass of the PEDOT incorporated into the film was monitored simultaneously using a quartz crystal microbalance and was also consistent with a successful polymerization (Figure 2A). In the first cycle, 15 μg of PEDOT and electrolyte were deposited per cm² of the working electrode's geometric area. The amount of deposited PEDOT increased to 30 μg cm^"2 for the second and subsequent cycles, up to 10 total cycles that were performed. FT-IR spectroscopy of the films conducted both before and after the electropolymerization indicate both the formation of PEDOT and that the DAAQ-TFP' s chemical linkages are retained. When the electropolymerization was performed for only two cycles, the FT-IR spectrum of the film is almost identical to that of as-synthesized DAAQ- TFP COF film. Both spectra exhibit a peak at 1250 cm^-1, 1560 cm^-1, and 1615 cm^-1 corresponding to intact β-ketoenamine C-N, C=C, and C=0 stretches, respectively. After nine polymerization cycles, spectral features resembling bulk PEDOT emerge and the β- ketoenamine stretches have lower relative intensities but are still present (Figure 2B).

Grazing incidence x-ray diffraction (GIXD) performed at the Cornell High Energy

Synchrotron Source indicated that the as-synthesized DAAQ-TFP films are crystalline, with the expected peak at 0.23 A^"1 that corresponds to the (100) reflection of the hexagonal lattice. This peak is also observed in films that were subjected to two electropolymerization cycles, indicating that the periodicity of the DAAQ-TFP thin film is retained under the

electropolymerization conditions. After nine cycles, this peak is not observed, which is not unexpected given that the electropolymerization involves the deposition of an amorphous organic polymer (PEDOT) into an ordered support (DAAQ-TFP COF). Such a processes is associated with decreased signals in GIXD experiment (Figure 2C).

[0090] XPS performed on a DAAQ-TFP COF film subjected to nine PEDOT electropolymerization cycles was also consistent with the formation of PEDOT in and / or on the COF host. The peaks for the Nis electrons were used as a marker for the DAAQ-TFP COF, and the S_2p peak was used to indicate the presence of PEDOT. XPS spectra were recorded after a series of exposures to an Ar ion beam that etches both materials, providing a quantitative measure of the amounts of each material as a function of film depth. Prior to etching, an intense S_2p signal is observed, along with no signal above baseline in the Nis region. Upon increased etching, the Nis peak is observed and the S_2p decreases in intensity but does not disappear (Figure 2D). These confirmed observations suggest that PEDOT is present, both on top of the DAAQ-TFP COF films and in their pores, when the

electropolymerization is performed for nine cycles under our experimental conditions.

[0091] The PEDOT / DAAQ-TFP COF composite film demonstrated an enhanced current response using cyclic voltammetry, as compared to an unmodified DAAQ-TFP COF film (0.5 M H2SO4, 20 mV s^"1 scan rate, Figure 3 A). In both CVs, we see highly reversible electrochemistry consistent with the rapid electron transfer to / from anthraquinones.

However, the PEDOT / DAAQ-TFP COF exhibits more than an order of magnitude increased current. These responses correspond to the storage of only 0.230 mC of charge for the as-synthesized DAAQ-TFP thin films and 9.3 mC for the PEDOT modified COF sample. Furthermore, the PEDOT-modified film retains its higher charge storage capacity at faster scan rates up to at least 500 mV s^"1. In contrast, the as-synthesized DAAQ-TFP thin film shows ca. 70% lower capacitance at scan rates greater than 100 mV s^"1 (Figure 3B). These experiments indicate that the electropolymerization of PEDOT in a redox-active COF film provides dramatically enhanced charge storage, capacity, and rate, most likely by improving the film's conductivity.

[0092] Encouraged by the CV experiments for the PEDOT / DAAQ-TFP COF system, we measured the film's capacitance using galvanostatic charge-discharge

experiments at various charging rates, C, where n C corresponds to the charging or discharging of the film's capacitance over the course of 1/n hours. PEDOT / DAAQ-TFP electrodes consistently show higher capacitances than the unmodified DAAQ-TFP COF, and maintain more than 80% of their capacitance when charged or discharged at 10 - 100 C, corresponding to charge times of 360 - 36 seconds, respectively. The PEDOT-modified

DAAQ-TFP film even retains up to 50% of its maximum capacity (350 F cm^"3) at the extremely high charging rate of 1600 C, corresponding to a charging time of 2.25 s (Figure 4A). In contrast, the unmodified COF films show only moderate capacitances at 10 C (20 F cm^"3), which decrease even further at higher charge / discharge rates.

[0093] The PEDOT-modified DAAQ-TFP COF films also show promising stability over the course of many charge-discharge cycles. For example, the capacitance of the film was recorded at 10 C for three cycles, then 100 C for 2250 cycles, and then three more cycles at 10 C. No decrease in capacitance is observed under these conditions, which is consistent with the long-term stability of the unmodified DAAQ-TFP COF film to at least 5000 cycles that we previously reported (Figure 4B).

[0094] The experiments described above demonstrate that EDOT can be

electropolymerized on a redox-active COF film. The resulting composite film shows both enhanced charge capacity and more rapid charging and discharging processes, making these systems of interest for electrical energy storage devices.

EXAMPLE 2

[0095] This example provides a description of methods of making and

characterization of conducting-polymer modified covalent organic frameworks of the present disclosure and films thereof. The example describes charge storage and power density of conducting polymer-modified covalent organic frameworks of the present disclosure.

[0096] In this example we enhanced the electrical conductivity of a redox-active 2D COF film by electropolymerizing 3,4-ethylenedioxythiophene within its pores. The resulting poly(3,4-ethylenedioxythiophene) (PEDOT)-infiltrated COF films exhibit improved electrochemical responses, including quantitative access to their redox-active groups, even for 1 μιη-thick COF films that otherwise provide poor electrochemical performance. PEDOT- modified COF films can accommodate high charging rates (10-1600C) without

compromising performance, and exhibit both a ten-fold higher current response relative to unmodified films and stable capacitances for at least 10,000 cycles. This work represents the first time that electroactive COFs or crystalline framework materials have shown volumetric energy and power densities comparable with other porous carbon-based electrodes, thereby demonstrating the promise of redox-active COFs for EES devices.

[0097] In this example we electropolymerized EDOT into the pores of redox-active

2D COF films. The resulting PEDOT-modified COF films (Figure 5) exhibit quantitative electrochemical accessibility of their redox-active groups and enable the use of at least 1 μπι thick films that can sustain fast charging rates (up to 1600C) without compromising performance. This improved performance relative to as-synthesized COF films corresponds to a thirty-fold increase in volumetric energy density and a twelve-fold increase in volumetric power density. Notably, in thin film capacitors, gravimetric capacitances are less meaningful than volumetric capacitance because the mass of the active material is often only a small fraction of the weight of the device, negligible and capacitances based on active material mass can be artificially high.

[0098] The electropolymerization of PEDOT within a nanoporous COF template represents a means to organize the conductive polymer at the nanometer length scale, which is an increasingly important capability for electrochromic, drug delivery, electrocatalytic, and EES devices, among other applications. Templated electropolymerizations form conducting polymers, such as polypyrrole, polythiophene, or polyaniline, as nanowire arrays, which respond rapidly in electrochemical devices largely because of short counter ion diffusion lengths. In these examples, the porous templates are removed. Here we observed a synergistic effect in which the pore-confined PEDOT effectively wires the redox-active groups of the COF to the electrode, enabling the use of thicker films and faster charging rates.

[0099] Results and Discussion. PEDOT was electropolymerized within a DAAQ-

TFP thin-film working electrode via cyclic voltammetry in a 100 mM CH3CN solution of EDOT containing 100 mM («-Bu NC104 (TBAP) as the supporting electrolyte. DAAQ-TFP thin films were prepared by adding a DMF solution of 2,4,6- triformylphloroglucinol (TFP) over 1 h to a DMF solution of DAAQ containing a gold substrate. We isolated poly crystalline thin films whose thickness was controlled by varying the initial monomer concentration. For example, an initial DAAQ concentration ([DAAQ]o) of 22 mM yielded DAAQ-TFP thin films of 810 ± 224 nm thickness, as determined by atomic force microscopy (Figures 10-13). The chemical composition of the COF films was assessed using FT-IR and X-ray

photoelectron spectroscopy (XPS). Their morphology was characterized by scanning electron microscopy (Figures 14 and 15), and their crystallinity was measured using grazing incidence x-ray diffraction (Figures 16-18). These measurements are consistent with those of thinner films and indicate the formation of crystalline DAAQ-TFP films whose layered crystallites are preferentially oriented parallel to the substrate (Figures 13-18). The amount of PEDOT incorporated into the 2D COF film was characterized by two independent measurements: the current passed during each electropolymerization cycle (-0.5-1.0 V vs. Ag/AgC104, 20 mV s^{" 1} scan rate) and the mass deposited onto a COF-modified electrode, as detected using an electrochemical quartz crystal microbalance (EQCM, Figure 2A and b). In the first cycle, 15 μg of PEDOT and electrolyte were deposited per cm² of the working electrode's geometric area, which increased to 30 μg cm^"2 for the second and subsequent cycles. Due to viscoelastic losses over the course of the experiment the Sauerbrey equation overestimates these masses (see below, Figures 19 and 20). During the reductive sweep of each electropolymerization cycle, there is a mass loss corresponding to removal of perchlorate counter ions (de-doping) from the film to maintain electroneutrality. The voltammetnc response exhibited an increase in current with each scan, which is characteristic of PEDOT electropolymerization (Figure 6B), and the redox processes occurred at voltages consistent with those expected for EDOT oxidation. FT-IR spectra of the films, acquired before and after the electropolymerization, suggest the formation of PEDOT and that the DAAQ-TFP' s chemical linkages are retained. After two electropolymerization cycles, the FT-IR spectrum of the film was almost identical to that of the as-synthesized DAAQ-TFP film. Both spectra exhibited peaks at 1250 cm^"1, 1560 cm^"1, and 1615 cm^"1, corresponding to intact ?-ketoenamine C-N, C=C, and C=0 stretches, respectively. After nine electropolymerization cycles, spectral features resembling bulk PEDOT emerged, though absorbances associated with the ?-ketoenamine remained, albeit with lower relative intensities (Figure 6C). Grazing incidence X-ray diffraction (GIXD) experiments, performed at the Cornell High Energy Synchrotron Source (CHESS), indicate that the as-synthesized DAAQ-TFP films are crystalline, with a peak at 0.23 A^"1 that corresponds to the (100) reflection of the hexagonal lattice. This peak was also observed in films that were subjected to two electropolymerization cycles, indicating that the periodicity of the DAAQ-TFP thin film is retained under the electropolymerization conditions. After nine cycles, this peak was not observed, which was not unexpected after depositing amorphous PEDOT within the ordered DAAQ-TFP COF (Figures 16-18). For example, it was previously reported that the scattered intensity diminishes when a porous host is filled with a polymer of similar electron density. The surface area of the films before and after PEDOT polymerization, as measured using Kr adsorption (Figure 21), was also consistent with the deposition of the polymer into the pores of the DAAQ-TFP COF. Unmodified

DAAQ-TFP films exhibited Brunauer-Emmett-Teller surface areas (SBET) of 73 cm² per cm² of substrate. This value decreased to 40 cm² per cm^"2 after two electropolymerization cycles, and films subjected to nine electropolymerization cycles appeared nearly nonporous (SBET = 6 cm² cm^"2). An X-ray photoelectron spectroscopy (XPS) depth profile of the elemental composition of a PEDOT-modified DAAQ-TFP film subjected to nine electropolymerization cycles further indicates the presence of PEDOT throughout the 2D COF film. XPS spectra were recorded after a series of exposures to an Ar ion beam that etches both the PEDOT and the COF. Prior to etching, an intense S_2p signal (164.9 eV) is observed, along with no signal above baseline in the N region (399.2 eV), which we attribute to a thin PEDOT overgrowth layer on top of the COF film. After the first etching cycle, Nu and S_2p signals are both observed in five subsequent consecutive spectra (Figure 6D) and, after prolonged etching, the entire film is removed. These combined observations indicate that PEDOT

electropolymerization occurs in the pores of the COF film, and that the conductive polymer effectively infiltrates the COF structure.

[0100] The PEDOT-modified DAAQ-TFP composite films exhibited dramatically enhanced current responses in cyclic voltammetry experiments when compared to an unmodified DAAQ-TFP film (0.5 M H₂S0₄, 20 mV s^_1 scan rate, Figure 7A). While both CVs exhibit reversible electrochemistry consistent with electron transfer between the anthraquinones and the working electrode, the PEDOT-modified DAAQ-TFP films exhibited more than an order of magnitude increased current. These responses correspond to a faradaic charge storage of only 0.230 mC, corresponding to only 3% of the available anthraquinones for a representative unmodified, 1 μπι-thick DAAQ-TFP film (see below for a sample calculation of electrochemically addressed anthraquinones, Figure 22). This value increased to 9.3 mC after the same DAAQ-TFP sample was modified with PEDOT, corresponding to a 40-fold increase in accessible charge. In contrast to the unmodified COF films, PEDOT- modified films retain their well-defined redox responses and charge densities at scan rates up to 500 mV s^"1 (Figure 7B). In contrast, the already small percentage of accessible

anthraquinones (3%) measured at 20 mV s^"1 decreased to less than 1% at sweep rates above 100 mV s^"1 (Figure 7B).

[0101] Having established an enhancement in performance associated with modifying

COF thin films with PEDOT, we determined the optimal electropolymerization conditions (9 cycles, 20 mV s^"1, see below for details Figures 23-25) for maximizing the charge stored and accessed at high scan rates (100-500 mV s^"1) while maintaining electrolyte access to the framework. While additional electropolymerization cycles increased the capacitance associated with additional PEDOT coverage, the faradaic contribution remained constant at a value corresponding to a quantitative access to the quinone sites (Figure 23). These experiments indicate that the electropolymerization of PEDOT in a redox-active COF film provides enhanced charge storage capacitance and rate. These effects most likely arise from intimately mixing PEDOT in the COF for improved conductivity of the PEDOT-modified DAAQ-TFP film, which was assessed using electrochemical impedance spectroscopy (EIS, Figures 26, 27, and Table 1). The PEDOT-modified DAAQ-TFP film, as well as a PEDOT film electropolymerized onto an unmodified Au substrate, exhibited electrical conductivities on the order of 10^"2 S m^"1. We used a two constant-phase-element (2CPE) model, in series with the solution resistance (Rs), to model the EIS data. The R_s was more than an order of magnitude lower for the PEDOT-modified DAAQ-TFP film (Rs = 20 Ω) than the unmodified DAAQ-TFP (Rs = 430 Ω), demonstrating an increased conductivity when PEDOT is incorporated into the films.

[0102] Given the electrochemical performance of the PEDOT-modified DAAQ-TFP films, their capacitance was evaluated through galvanostatic charge-discharge experiments performed at various charging rates (C), where nC corresponds to charging or discharging of the film over \ln hours (Figures 28-33, Table 2). PEDOT-modified DAAQ-TFP electrodes consistently showed higher capacitances than those lacking PEDOT and retained more than 80% of their capacitance when charged or discharged at 10 and lOOC, corresponding to charge times of 360 and 36 seconds, respectively. The PEDOT-modified DAAQ-TFP film even retains 50% of its maximum capacitance (350 F cm^"3) at the extremely high charging rate of 1600C, corresponding to a charging time of only 2.25 s (Figure 8 A). In contrast, the unmodified DAAQ-TFP films show only moderate capacitances at IOC (20 F cm^"3), which decreased further at higher charge/discharge rates. The PEDOT-modified DAAQ-TFP films also showed desirable stability over 10,000 charge-discharge cycles (Figure 8B). The capacitance of the film was measured at IOC for three cycles, then at lOOC for 10,000 cycles, and finally three more cycles at IOC. No decrease in capacitance was observed under these conditions. To further probe the stability, we conducted a potentiostatic experiment where we held the composite film at a reducing potential (-0.3 V vs Ag/AgCl) for 15 h, after which no degradation in the CV response was observed, Figure 34). We examined the possibility for slow internal electron transfer between the PEDOT in its oxidized, conducting form and the reduced anthraquinone moieties by performing a scan rate dependence experiment at slow cycling rates (0.5, 1, 5, 10, 20, 50, 100, 300, 500 mV s^"1). Since the integrated charge for anthraquinone reduction is greater than that of the integrated oxidative wave, we hypothesize that a portion of the reduced anthraquinone moieties transfer electrons and reduce the oxidized PEDOT (effectively a "self-discharge" mechanism). However, the coulombic efficiency becomes quantitative at scan rates above 10 mV s^"1 suggesting that process is not occurring at the operational C rates and is not detrimental to the composite electrode performance (see Figure 35 and accompanying discussion).

[0103] To determine the relative contributions of the faradaic and non-faradaic processes at both fast and slow scan rates, GCDC experiments were performed between 0.35-0.6 V vs. Ag/AgC10₄, where the DAAQ moieties are redox-inactive, and compared them to an experiment performed over the full -0.3-0.6 V vs. Ag/AgC10₄ range (Figure 31, Table 2). This comparison indicates that both the DAAQ moieties and the PEDOT contribute nearly equally to the capacitance goat all tested charging rates, demonstrating the synergistic effect of combining the two materials. We also examined the performance of a PEDOT composite of a non-redox-active COF based on 1,4-diaminobenzene (DAB), DAB-TFP

COF, which showed capacitances comparable to PEDOT contribution of the PEDOT- modified DAAQ-TFP composite (Figure 32). Furthermore, Au electrodes modified only with electropolymerized PEDOT exhibited a similar double-layer capacitance as the PEDOT/COF hybrid, but lacked the enhanced charge storage associated with the DAAQ redox couple, as determined from the lack of voltage plateau in the potential/capacity plots (Figure 29 and 30).

[0104] As described previously, performance metrics are more appropriately evaluated using a two electrode configuration; therefore, we probed the PEDOT-modified DAAQ-TFP films using a high surface area carbon counter and quasireference, where the size and mass of the carbon counter was significantly greater than that of the active film. Under these conditions (20 mV s^"1, 0.5 M H2SO4) the films exhibit reversible oxidation and reduction waves (Figure 8C) that are associated with pseudocapacitive features in a two- electrode configuration. GCDC profiles exhibited well-defined voltage plateaus consistent with previous experiments described herein (Figure 8D) and capacitances comparable to those observed in a three-electrode system at charging rates up to 800C. At still faster charging rates, device performance was limited by the counter electrode, not the COF film (Figure 36).

[0105] As a proof-of-principle for integrating larger amounts of the COF into devices, we fabricated coin cell devices, which were characterized and used to power a light emitting diode (LED, Figure 8E). Since the quantity of the PEDOT-modified COF obtained from electropolymerization is of the order of micrograms, we turned to insoluble polycrystalline DAAQ-TFP COF powder and a Fe(C10₄)3 chemical polymerization of EDOT within the pores to afford bulk PEDOT-modified DAAQ-TFP COF (see below for fabrication procedures, Figures 37-41, and Table 3). The crystallinity and chemical composition of these materials were confirmed using X-ray powder diffraction and IR spectroscopy (Figures 38 and 39). A 4 mg portion of PEDOT-modified DAAQ-TFP COF powder (1 : 1 PEDOT/COF by mass as active electrode and activated carbon counter electrode) was integrated into coin cells. When two of these cells were connected in series, they successfully powered a green LED for 30 s. Electrochemical performance testing of the cells show that they exhibit well- defined redox waves associated with the reduction and oxidation of the anthraquinone moieties in both the CV and GCDC responses (Figures 41 and 42) with a capacitance of 197 F g^"1 based on the active composite electrode or 30 F g^"1 when the mass of the active and counter electrodes are considered. Notably, these cells are not optimized and the gravimetric capacitances are expected to increase by identification of the minimal mass of counter electrode and PEDOT to elicit the same electrochemical performance. However, they demonstrate a means to fabricate working charge storage devices from conducting polymer- modified COFs, even as methods to access thicker films continue to emerge.

[0106] Conclusions. Previously described 2D COFs had shown promise for EES devices only when used either as few-layer sheets or very thin films (-50 nm) because of their limited conductivity. Although some coordination polymers circumvent this issue through elegant linkage chemistries, such approaches limit the scope of accessible frameworks. The facile electropolymerization of EDOT within the pores of comparably thick COF films (~1 μπι) enhances the framework's conductivity to provide complete electrochemical

addressability of redox-active groups within the COF, even at very high scan rates. The complete electrochemical accessibility and fast charging rates of the COF/PEDOT

composites show significant improvements in volumetric energy and power densities relative to unmodified COF films, as well as desirable stability to cycling.

[0107] Synthesis of DAAQ-TFP Films: DAAQ (17 mg, 0.071 mmol) in

N,N-dimethylformamide was added to a glass vial. A gold electrode (2.5 cm x 1.3 cm) was submerged in the solution, and a septum was used to seal the vial. The solution was placed on a hotplate preheated to 90 °C. Subsequently, TFP (10 mg, 0.048 mmol) was added over the course of one hour via syringe from a 10 mg mL^"1 solution in DMF. During the course of the addition, the reaction mixture was gently swirled. After the addition, the reaction was allowed to proceed at 90 °C for an additional 3 h. The total reaction time was 4 h (including TFP addition), and the final volume was 4.2 mL after TFP addition. After the reaction was complete, the film which covered electrode was removed, rinsed three times with DMF and twice with acetone then dried in air.

[0108] Electropolymerization of 3,4-ethylenedioxythiophene (EDOT):

Electropolymerization was carried out in a standard three electrode set up under an argon atmosphere with a DAAQ-TFP COF film on gold (prepared as described above) as the working electrode, a Ag/AgC10₄ reference electrode, and either a coiled Pt wire or high surface area carbon counter electrode. A controlled area (0.64 cm²) surface cell was used for electrochemistry experiments. A 0.1 M solution of EDOT was prepared in 0.1 M TBAP, and nine electropolymerization cycles between -0.5 and 1.1 V vs Ag/AgC10₄ at 20 mV s^"1 were carried out. After electropolymerization the PEDOT-modified DAAQ-TFP on gold was rinsed 3x with acetonitrile and 2x with acetone before electrochemical testing.

[0109] Height analysis of films: AFM was used to determine film thicknesses both before and after electropolymerization of EDOT. Film heights were obtained from averaging step edges at three locations on the film (see below for further details).

[0110] Electrochemical testing of PEDOT-modified DAAQ-TFP films: After electropolymerization, the prepared films were rinsed as described above and submerged in 0.5 M H2SO4. For initial testing, cyclic voltammetry with scan rate dependence, or galvanostatic charge/discharge experiments were performed in a three electrode

configuration. Capacitances were obtained from the discharge curves by multiplying the applied current by the time of discharge and normalizing by the examined voltage window and geometric film volume. Film volumes were obtained from the electrochemical cell area and the experimentally determined film thicknesses as described above. Sample calculations can be found below. Thin films were also tested in a two-electrode thin film set-up where films were countered to a high surface area carbon after shorting the reference and counter electrode together. Sample calculations for volumetric capacitance and electrochemically accessible anthraquinones can be found below.

[0111] A. Materials and Instrumentation. All reagents were purchased from commercial sources and used without further purification. N,N-dimethylformamide was purchased from Sigma Aldrich and purified using a custom-built alumina column-based solvent purification system.

[0112] Infrared (IR) spectra were recorded on a Thermo Nicolet iSlO with a diamond

ATR attachment or on a Bruker Vertex 80V with a Germanium ATR attachment and are uncorrected.

[0113] Grazing incidence X-ray diffraction (GIXD) was performed at the G2 station at Cornell High Energy Synchrotron Source (CFIESS) using a beam energy of 11.25 ± 0.01 keV (λ = 0.1103 nm), selected using a single-crystal Be crystal monochromator. Motorized slits were used to define a 0.2 ^χ 3 (VxH) mm² beam. The data were collected using a 640- element ID diode-array, of which each element incorporates its own pulse counting electronics capable of count rates of -105 photons s^"1. A set of 0.1° Soller slits were used on the detector arm to define the in-plane resolution. The scattering geometry is described in detail elsewhere.¹ Each data set was collected by scanning the detector with the sample stationary. The incidence angle, a, between the beam and sample surface was 0.340°. Axes labels Q-L and Q are defined using the GISAXS convention Q-L = 4 / sin(5/2) and Qj = 4 / sin(v/2), where δ and v are the vertical and horizontal scattering angles, respectively. At α=δ=0, hQ|| and h Q-L (where h is Planck's constant) are the components of momentum transfer parallel and perpendicular to the sample surface, respectively.

[0114] Atomic force micrographs (AFMs) were taken on an Asylum MFP-3D-BIO operating in tapping mode and equipped with a Tap300DLC diamond-like carbon or Tapl50Al-G Si tip with aluminum reflex coating (tip composition was not seen to affect image quality).

[0115] X-ray photoelectron spectra (XPS) were taken using a Surface Science

Instruments SSX-100 system with operating pressure ~2xl 0^"9 Torn Monochromatic A1K- alpha x rays (1486.6 eV) were used with beam diameter of 1 mm. Photoelectrons were collected at a 55° emission angle. A hemispherical analyzer determined electron kinetic energy, using a pass energy of 150 V for wide/survey scans, and 50 V for high resolution scans. A flood gun was used for charge neutralization of non-conductive samples.

[0116] Surface area measurements were conducted on a Micromeritics ASAP 2020 Accelerated Surface Area and Porosimetry Analyzer using eight 1 μιη thick DAAQ-TFP COF films. Samples were degassed at 80 °C for 2 hours. Krypton isotherms were generated by incremental exposure to ultra high purity krypton up to P/Po of 0.4 over 12-hour periods in a liquid nitrogen (77K) bath. Surface parameters were determined using BET adsorption models (Micromeritics ASAP 2020 VI .05).

[0117] Electrochemical-Quartz Crystal Microbalance (EQCM) experiments were performed using a Stanford Research Systems QCM 200 interfaced to a Princeton Applied Research Versastat3 potentiostat. DAAQ-TFP COF was grown on O100RX3 quartz resonators (Au with Ti adhesion layer) using the slow addition method described below. A water-jacketed beaker was used to maintain a constant temperature of 25 °C during the EQCM experiment. The changes in mass and resistance were monitored over the

experimental time. A 100 mL solution of 0.1 M EDOT in a 0.1 M tetrabutyl ammonium perchlorate (TBAP)ZMeCN supporting electrolyte was used for the electropolymerization with a carbon counter electrode. Potentials were referenced to a Ag/AgC10₄ reference electrode.

[0118] Electrochemistry experiments were conducted on a Princeton Applied

Research VersaSTAT 3 potentiostat using a standard three electrode cell configuration, a 27 gauge Pt wired coiled or high surface area carbon as the counter electrode, and either an aqueous Ag/AgCl or organic Ag/AgC10₄ (standardized against Fc/Fc⁺) reference electrode. For the 0.5 M H2SO4, milliQ purified water was used. The 0.1 M TBAP supporting electrolyte was prepared using electrochemistry grade tetrabutylammonium perchlorate that was recrystallized from ethyl acetate, and anhydrous acetonitrile (Sigma Aldrich), which was stored over activated 3 A sieves.

[0119] B. S nthetic Procedures

Synthesis of 1,3,5-triformylphloroglucinol, TFP: TFP was synthesized following a previously reported procedure and characterization matched that in the literature.

[0120] Synthesis of DAAQ-TFP Films: Crystalline film growth: To a glass vial, a DAAQ (17 mg, 0.071 mmol) in N,N-dimethylformamide was added. A gold electrode (2.5 cm x 1.3 cm) was submerged in the solution and a septum cap placed on the top of the vial.

The solution was placed on a preheated 90 °C hotplate. Subsequently, TFP (10 mg, 0.048 mmol) was added over the course of one hour via syringe from a 10 mg mL^"1 solution in

DMF. During the course of the addition, the reaction mixture was gently swirled. After the addition the reaction was allowed to heat at 90 °C for an additional 3 hours. The total reaction time was 4 hours (including TFP addition) and final volume was 4.2 mL (after TFP

addition).

[0121] Electropolymerization of 3,4-ethylenedioxythiophene (EDOT): The electropolymerization was performed in a standard three-electrode configuration under an Ar atmosphere. The cell consisted of a DAAQ-TFP COF film on gold (prepared as described above) as the working electrode, a Ag/AgC10₄ reference electrode, and either a coiled Pt wire or high surface area carbon counter electrode. A controlled area (0.64 cm²) surface cell was used for electrochemistry experiments. A 0.1 M solution of EDOT was prepared in 0.1 M TBAP, and nine electropolymerization cycles between -0.5 and 1.1 V vs Ag/AgC10₄ at 20 mV s^"1 were performed. A nine-cycle polymerization passes the oxidative potential 10 times, because the initial cycle starts from open circuit, which is approximately 0.2 V vs Ag/AgC10₄. The counter electrode was placed in the same location relative to the working electrode during electropolymerization (c.a. 2 cm separation). After electropolymerization, the working electrode was rinsed three times with acetonitrile and two times with acetone prior to its electrochemical testing.

[0122] C. Atomic Force Microscopy (AFM). AFM images were processed using Gwyddion 2.34 software. The image was leveled, such that the exposed substrate surface was flat as shown by the height profiles below. Heights were calculated using an areal mask over the film surfaces. Step edges were achieved by scratching the DAAQ-TFP / PEDOT composite carefully so as to avoid scratching the underlying gold surface. On each film, three locations were analyzed and then averaged to give the film height. The height profiles displayed below demonstrate that a clean step edge was obtained and that the film was leveled appropriately.

[0123] F. Quartz Crystal Microbalance (QCM).

The Sauerbrey mass of the electrodeposited PEDOT was calculated using the Sauerbrey equation Af is the frequency change, fo is the resonant

frequency, Am is the change in mass, A is the piezoelectric active area, p_q is the density of quartz, and [iq is the shear modulus of the quartz. During the electropolymerization of EDOT, there is a linear increase in Sauerbrey mass accompanied by a corresponding linear increase in resistance. This resistance increase indicates that viscoelastic losses increase during the electropolymerization, such that the Sauerbrey mass represents an upper limit of the deposited gravimetric mass of the PEDOT. We find that the change in frequency for a given resistance change is roughly identical for each cycle, such that the overestimated mass is still proportional to the actual mass throughout the electropolymerization.

[0124] H. Electrochemical Methods and Data. Analyses were performed in a standard three electrode set up: a DAAQ-TFP film modified gold substrate, a Ag/AgCl or a

Ag/AgC10₄ reference, and a coiled Pt wire or high surface area carbon counter. All experiments were performed after purging the electrolyte with argon. Electropolymerization was carried out using 0.1 M EDOT in 0.1 M TBAP / MeCN via cyclic voltammetry between -0.5 and 1.0 V vs Ag/AgC10₄. The composite films were studied in 0.5 M H₂S0₄.

[0125] Electropolymerization was optimized at nine cycles (20 mV s^"1, 0.1 M EDOT / 0.1 M TBAP / MeCN, Figures 23 and 24). When the electropolymerization was carried out for two or five cycles, the amount of charged stored in the films was less than the theoretical (assessed through integration of the anthraquinone oxidation peak). When an 18 cycle polymerization was tested, the amount of charge stored in the film diminished with increased scan rate indicating poor access to the anthraquinones. This is consistent with densely polymerizing and overloading the COF with PEDOT such that electrolyte and counter ions cannot "keep up" with the redox-processes at the higher scan rates. This is seen in the CV response labeled " 18" in Figure 23 where the peaks associated with the anthraquinones are no longer well defined above PEDOT background. When EDOT is polymerized at a slower scan rate (2 mV s^"1, Figure 24) we also see poorly defined redox waves with an overall resistive response.

[0126] Approximation of Quinones Accessed in films (sample calculations)

(1) Determine unit cells of DAAQ-TFP COF exposed in the electrochemistry cell.

Unit cell area: 770 A²

Exposed geometric area in echem cell: 0.64 cm²

6.4 xio ⁵ m²

Number of unit cells in echem cell: = 8.3 X 10¹² unit cells

7.7 xlO^-18 m²

(2) Each unit cell provides one anthraquinone, so 8.3 X 10¹² quinones are exposed providing 1.6 X 10¹³ electrons or 2.7 X 10^-11 moles of electrons

(3) Each mole of elec re, each layer will provide

2.7 x 10^-11 moles

(4) Convert this charge to charge per nm

, L \ n nmm \\ -^" 1 μC

2.7 X 10^~6 0.362 = 7.4

layer/ \ layer/ nm (5) From AFM determine the thickess. For Figure 7, film thickness of 1300 nm.

(6) Multiply by the charge per nm to get theoretical percent of anthraquinones

7.4— (1300 nm) = 9.6 mC

nm

(7) Ratio the integrated oxidation charge from Figure 35 to the theoretical charge.

[0127] Table 1. Fitting parameters for PEDOT / DAAQ-TFP COF and DAAQ-TFP

COF. R_S E_S R_DL ERDL CPEDL E_DL RCT E_RCT CPE_CT E_CT (Ω) (Ω) (Ω) (Ω) (mF) (mF) (Ω) (Ω) (mF) (mF)

Substrate

PEDOT- modified

19.7 0.32 22 0.17 400 0.01 21336 4547 4.7 0.023 DAAQ- TFP COF

unmodified

0.003

DAAQ- 451.6 1.89 1696 338 0.053 9976 5110 0.13 0.018

9

TFP COF

[0128] Table 2. Percent of capacitance contribution from nonfaradaic region as assessed through the GCDC experiment.

C-rate Percent nonfaradaic

10 65

20 61

50 61

100 58

200 56

400 49

800 52

1600 40 [0129] Sample calculation for volumetric capacitance. Capacitances were calculated from galvanostatic charge-discharge experiments using the discharge potential- time curve by multiplying the applied current by the discharge time to give A*s then dividing by the potential range and geometric volume of the electrode to give mF cm^"3. The applied current was determined by integrating the oxidative half of the cyclic voltammogram of the PEDOT / DAAQ-TFP COF film to give charge in mA»s. A rate of 10 C was determined by dividing the charge by 360 s. Each profile shows a voltage plateau around the E₀' of the anthraquinone moieties.

(1) Determine the elapsed time of discharge (oxidation of anthraquinones) Δΐ = 145 s

(2) Multiply this by the applied current to get charge: 145 s (136 μΑ) = 0.01972 A*s = 0.01972 C (3) Divide this by the potential window the oxidation sweep occurs in: 0.01972 C / 0.9 V

0.022 F

(4) Normalize by the geometric volume for a given film. In this example 1005 nm, which is a volume of 6.4 x 10^"5 cm^"3: 0.022 F / 6.4 x 10^"5 cm^"3 = 341 F ern^"3 [0130] At very slow sweep rates the coulombic efficiency is less than quantitative, suggesting a form of self-discharge in the system. In order for the PEDOT to access the DAAQ groups within the COF, it must be in the doped (conducting) state. In fact, that was one of the reasons why we chose PEDOT as the electronically conducting polymer since its onset potential for doping is negative of the formal potential of the DAAQ groups. The onset potential for PEDOT doping depends on a number of variables including solvent and polymer chain length. However, it is generally negative of 0.0 V vs Ag/AgCl as is evident in Figure 7. However, the formal potential for oxidation of the DAAQ groups is only slightly positive of the onset of PEDOT doping. Thus, the PEDOT is not fully doped at potentials where DAAQ begins to be oxidized. This means that there can be some extent of "operationally" self- discharge especially at very slow sweep rates since the electrode would be effectively "spending more time" in the potential region where these processes would be operative.

[0131] Figure 43 demonstrates that DAAQ-TFP COF is physically mixed via grinding with PEDOT to prepare a slurry modified electrode similar to our previous preparation,³ the conducting polymer does not infiltrate the pores and is not intimately mixed with the COF. This CV response provides further support that both the chemical and electrochemical polymerization of EDOT is filling the pores of the DAAQ-TFP COF.

[0132] Estimation of the mass of a 500 nm thick DAAQ-TFP COF film

(1) Geometric exposed electrochemistry cell area = 0.64 cm²

(2) Number of unit cells per echem cell:

From the unit cell

Area = 25.8 A (29.8 A)

= 770.7 A² = 7.7 x 10^"14 cm² per unit cell

(ii) Number of cells = (geometric area of cell) / (area of unit

.64 cm²) / (7.7 x 10^"14 cm²) = 8.3 x 10¹² unit cells

(iii) Number of moles = 8.3 x 10¹² unit cells / 6.022 x 10²³ = 1.4 x 10^"11 mol (3) Mass of unit cells in layer:

1026 g mol^"1 (1.4 x 10^_11 mol) = 1.4 x 10^-8 g per layer

(4) Accounting for thickness: 5000 A / 3.6 A = 1388 layers

1388 layers (1.4 x 10^"8 g / layer) = 19 μg

(5) Including PEDOT

11 μg cm^"2 + 8(20 μg cm^"2) = 171 μg cm^"2

171 ug cm^"2(0.64 cm²) = 109 μg

[0133] Device Preparation/Assembly. PEDOT modified DAAQ-TFP COF powder or coin cell preparation: The 10: 1 and 1 : 1 PEDOT/COF composites were synthesized via chemical oxidation of EDOT in the presence of DAAQ-TFP COF powder. A 43 mg portion of EDOT was added into a mixture COF powder (30 mg) in methanol (MeOH) at 0 °C. After 15 minutes of mixing, Fe(C10₄)3 (0.214 g) was dissolved in MeOH and slowly added to the mixture of COF and EDOT. After stirring for 6 hours, dark blue powder was obtained. The polymer was extensively washed using MeOH to remove traces of Fe(C10₄)3 and dried at 90 °C overnight.

[0134] Coin-shaped electrodes of both cathode (PEDOT/COF) and anode (activated carbon, AC) were prepared by adding 90 mg of material (for cathode, 80 mg of PEDOT/COF + 10 mg Super P carbon, for anode 90 mg of activated carbon) to a scintilation vial that is equipped with a stir bar and 10 mg of polytetrafluoroethylene (PTFE) as a binder. Less than 1 mL of ethanol was added and the mixture was allowed to vigorously mix at 60 °C until the mixture is almost dry. The gels were rolled into a thin film and was allowed to dry at 60 °C overnight.

[0135] Cell Assembly and Working A lithium-ion battery CR2032 cell was used as the device chamber, and was assembled, by stacking a Ti-foil, PEDOT/COF (cathode), separator, activated carbon, Ti-foil, stainless steel, spring and a cap (Figure 32). The diameters of the components may be found in Table 3. CV characterization of single coin cell device was tested by contact using Cu tape. After individual cells were confirmed to be working, two cells were connected in series using Arbin channels connect by wires (Figure 23F). In order to charge a 2.2 V LED, the setup was charged to 2.2 V for 10 s, then was allowed to relax until the LED dimmed completely (about 30 s).

[0001] Table 3. Dimensions of cell components

Component Ti current PEDOT / DAAQ-TFP Anode Separator

collector COF (1:1)

Diameter (in) 7/16 5/16 5/16

Claims

CLAIMS:

1. A composition comprising one or more covalent organic framework layers with conducting polymer, at least partially, disposed in the pores and/or surface of the covalent organic framework layers.

2. The composition of claim 1, wherein the conducting polymer comprises one or more redox active compounds and/or moieties derived from one or more redox active compounds.

3. The composition of claim 2, wherein the conducting polymer comprises at least two different redox active compounds and/or moieties derived from one or more redox active compounds.

4. The composition of claim 1, wherein the one or more covalent organic framework layers comprise one or more redox active compounds and/or moieties derived from one or more redox active compounds.

5. The composition of claim 4, wherein the one or more one or more redox active compounds and/or moieties derived from one or more redox active compounds are covalently attached to the one or more covalent organic framework layers.

6. The composition of any one of claims 2 or 4, wherein the redox active compounds are independently at each occurrence in the polymer are selected from the group consisting of:

- 52 - wherein R is H, alkyl, or wherein R is H, alkyl, or aryl, a aryl, and and

R₂ is H, alkyl, or aryl R₂ is H, alkyl, or aryl

wherein R is H, alkyi, or aryl, wherein R is H, alkyi, or HN NH HN N- and aryl, and

R₂ is H, alkyi, or aryl R₂ is H, alkyi, or aryl o o o o

wherein R is H, alkyi, or aryl wherein R is H, alkyi, or aryl wherein R is H, alkyi, or aryl

X₂ s H, alkyl, aryl, or halide,

wherein X is H, alkyl, aryl, or halide, x₃ s H, alkyl, aryl, or halide,

X₂ is H, alkyl, aryl, or halide, x₄ s H, alkyl, aryl, or halide,

X₃ is H, alkyl, aryl, or halide, and x₅ s H, alkyl, aryl, or halide, and s. X₄ is H, alkyl, aryl, or halide x₆ s H, alkyl, aryl, or halide



X is halide, -SH, -NH₂, -OR, wherein R is a C-| to wherein R is H, alkyl, or aryl C₂₀ alkyl group

wherein n is independently at each occurrence in the composition 1 to 12, alkyl is independently at each occurrence in the composition a Ci to C20 group, and aryl is independently at each occurrence in the composition a C5 to C20 group, and halogen at each occurrence in the composition is -F, -CI, -Br, or -I.

7. The composition of claim 1, wherein the conducting polymer is poly(3,4- ethylenedioxythiophene) PEDOT.

8. The composition of claim 1, wherein at least one of the covalent organic framework layers comprises 2,6-diaminobenzene (DAAQ) moieties and 1,3,5- triformylphluroglucinol (TFP) moieties.

9. The composition of claim 1, wherein at least one of the covalent organic framework layers comprises TFP moieties.

10. The composition of claim 1, wherein at least one of the covalent organic framework layers comprises DAAQ moieites.

11. The composition of claim 1, wherein the pores of one or more of the one or more covalent organic framework layers have a dimension of 2 mm to 50 nm.

12. The composition of claim 1, wherein the surface area of one or more of the one or more of the covalent organic framework layers is 500 m²/g to 2500 m²/g.

13. The composition of claim 1, wherein the composition is in the form of a thin film.

14. The composition of claim 13, wherein the thin film is disposed on at least a portion of a substrate.

15. The composition of claim 14, wherein the substrate is a metal substrate or metal- coated substrate.

16. A method for making one or more covalent organic framework layers with conducting polymers, at least partially, disposed in the pores and/or surface of the covalent organic framework layers:

electropolymerizing a conducting-monomer in the presence of one or more COF layers,

wherein the one or more conducting-polymer modified COF layers are formed.

17. An electronic device comprising one or more covalent organic framework layers with conducting polymers, at least partially, disposed in the pores and/or surface of the covalent organic framework layers.

18. The electronic device of claim 17, wherein the device is selected from the group consisting of batteries and capacitors.

19. The electronic device of claim 18, wherein the capacitor is a super capacitor.