Design of Photothermal Covalent Organic Frameworks by Radical Immobilization

Abstract

Open AccessCCS ChemistryRESEARCH ARTICLE5 Aug 2022Design of Photothermal Covalent Organic Frameworks by Radical Immobilization Xiaohui Tang†, Zhongxin Chen†, Qing Xu, Yan Su, Hong Xu, Satoshi Horike, Huanhuan Zhang, Yuan Li and Cheng Gu Xiaohui Tang† State Key Laboratory of Luminescent Materials and Devices, Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology, Guangzhou 510640 , Zhongxin Chen† State Key Laboratory of Luminescent Materials and Devices, Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology, Guangzhou 510640 , Qing Xu *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute (SARI), Chinese Academy of Sciences (CAS), Shanghai 201210 , Yan Su State Key Laboratory of Luminescent Materials and Devices, Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology, Guangzhou 510640 , Hong Xu Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 , Satoshi Horike Institute for Integrated Cell-Material Sciences, Institute for Advanced Study, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501 , Huanhuan Zhang State Key Laboratory of Luminescent Materials and Devices, Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology, Guangzhou 510640 , Yuan Li *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] State Key Laboratory of Luminescent Materials and Devices, Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology, Guangzhou 510640 Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates, South China University of Technology, Guangzhou 510640 and Cheng Gu *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] State Key Laboratory of Luminescent Materials and Devices, Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology, Guangzhou 510640 Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates, South China University of Technology, Guangzhou 510640 https://doi.org/10.31635/ccschem.021.202101198 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Covalent organic frameworks (COFs) characterized by structural diversity, face-to-face stacking and open channels exhibit unique advantages as photothermal materials but have rarely been applied in solar-driven water evaporation due to complicated framework design, tedious synthesis, and low solar-to-vapor efficiency. Herein, we report a materials design strategy to produce efficient and robust photothermal COF by anchoring nonemissive radicals to the pore surface by a [2+2] cycloaddition–retroelectrocyclization reaction. The radical COF not only possesses the features of COFs such as crystallinity, porosity, and chemical robustness, but also the characteristics of radicals including high spin density and extended absorption to the near-infrared region, which endow the radical COF with outstanding photothermal properties. The radical COF achieves exceptional temperature increment and good photostability upon irradiation with an 808-nm laser, exhibits solar-to-vapor efficiency up to 90.7%, and is adaptable for efficient seawater desalination. Our results provide a new design strategy for the facile production of COF-based photothermal materials. Download figure Download PowerPoint Introduction Covalent organic frameworks (COFs) are an emerging class of crystalline and porous polymers that allow π-conjugated organic building blocks to be covalently assembled into ordered structures.1–3 The most important feature of COFs is their designability, in which the different functional units can be introduced into COFs directly via de novo syntheses or postsynthetic strategies. These COFs have been shown useful in various applications such as gas capture, chemical sensor, ion conduction, electrocatalysis, and photocatalysis.4–19 COFs are promising candidates for photothermal materials since the face-to-face stacking of COF layers largely decreases the radiative decay and increases the nonradiative decay, while diverse organic units and chemical doping methods can be involved in the COF platforms to encode radical, charge-transfer (CT), and ionic species, which possess broad absorption extending to the near-infrared (NIR) region but are emission-prohibited, to the COF skeletons.20–24 However, up to now, the above-mentioned strategies have encountered several critical obstacles involving complicated framework design, tedious synthesis, low crystallinity, and unstable doped states. Developing a rational and simple design strategy to produce crystalline photothermal COFs with high photothermal efficiency and photostability is long awaited, but the current design approaches are inaccessible for this purpose. Here, we demonstrate a postsynthesis design strategy to produce photothermal COFs by a [2+2] cycloaddition–retroelectrocyclization (CA–RE) reaction. To the best of our knowledge, constructing functional COFs based on the CA–RE reaction has not yet been investigated. The targeted COF, termed GT-COF-3, immobilizing quinoidal radicals on the side chains, displays high crystallinity and chemical stability and converts the initial COF, which barely shows any photothermal performance, to outstanding photothermal COFs. Both the COF synthesis and postmodification are readily achieved and adaptable for scale-up production. The cyanovinyl decorative groups that we introduce exhibit unique radical characters in their ground states and endow the resulting COFs with broad absorption spectra from 250 to 1400 nm. We establish an interfacial heating-evaporation system based on the photothermal COFs, which yields solar-energy-to-vapor efficiency of 90.7% and a water evaporation rate of 1.314 kg m−2 h−1 under 1 sun irradiation. Moreover, the photothermal COFs were efficient for seawater desalination. Our results show that complicated skeleton design is not necessary for high-performance photothermal COFs, and the strategy of introducing appropriate radical side chains by easy synthetic approaches is a promising new option for future photothermal COFs. Experimental Methods Materials 1,3,5-Tri(4-aminophenyl)benzene (TPB), 2,5-bis(2-propynyloxy)terephthalaldehyde (BPTA) were purchased from Jilin Chinese Academy of Sciences-Yanshen Technology Co., Ltd. (Jilin, China). 4-ethynylanisole (98%, TCI, Chinese Agency Company of Energy Chemical, Shanghai, China), tetracyanoethylene (TCNE) (98%, TCI, Chinese Agency Company of Energy Chemical, Shanghai, China), acetic acid (99.5%, TCI, Chinese Agency Company of Energy Chemical, Shanghai, China), o-dichlorobenzene (o-DCB) (99.8%, Aldrich, Chinese Agency Company of Energy Chemical, Shanghai, China), anhydrous tetrahydrofuran (THF) (99.5%, Energy Chemical, Shanghai, China), n-butanol (n-BuOH) [high-performance liquid chromatography (HPLC), Fisher], anhydrous dichloromethane (DCM) (99.5%, Energy Chemical, Shanghai, China), anhydrous alcohol (99.5%, Energy Chemical, Shanghai, China), N,N-dimethylformamide (99.8%, Energy Chemical, Shanghai, China), and deuterated solvents (Energy Chemical, Shanghai, China) for NMR were purchased and used without further purification. CO2 (99.9999%) was purchased from MULAI Company (Guangzhou, China). Synthesis of molecular analog 1 A mixture of TCNE (1.5 mmol, 192.7 mg), 4-ethynylanisole (1 mmol, 132.1 mg), and DCM (6 mL) was degassed and recharged with nitrogen. After being stirred and refluxed for 16 h, the solvent was evaporated in vacuum, and the product was purified by column chromatography (eluent: DCM) to obtain 260.1 mg of a red solid (yield: 99%). 1H NMR (400 MHz, chloroform-d, δ) (ppm): 8.02 (s, 1H), 7.47–7.43 (m, 2H), 7.11–7.07 (m, 2H), 3.92 (s, 3H). 13C NMR (101 MHz, chloroform-d, δ) (ppm): 55.85, 88.99, 98.14, 108.51, 111.24, 111.64, 111.81, 115.76, 122.36, 131.49, 153.39, 161.44, 164.66. Atmospheric pressure chemical ionization mass spectrometry (APCI-MS) (m/z): [M]+ calcd for C15H8N4O, 260.26; found 261.2. Synthesis of TPB-BPTA-COF An o-DCB/n-BuOH (0.5 mL/0.5 mL) mixture of TPB (0.080 mmol, 28.1 mg) and BPTA (0.120 mmol, 29.1 mg) in the presence of an acetic acid catalyst (6 M, 0.1 mL) in a Pyrex tube (10 mL) was degassed via three freeze–pump–thaw cycles. The tube was flame-sealed and heated at 120 °C for 3 days. The precipitate was collected via centrifugation, washed six times with THF and then subjected to Soxhlet extraction with THF for 1 day to remove trapped guest molecules. The powder was collected and dried at 120 °C under vacuum overnight to produce TPB-BPTA-COF in an isolated yield of 77%. Synthesis of GT-COF-3 TPB-BPTA-COF (100 mg) and TCNE (100 mg) were placed in a 20-mL Schlenk tube, with spatial separation maintained to prevent the two from directly contacting each other (e.g., by holding TCNE in a smaller tube sealed at one end). The Schlenk tube was degassed and then was placed in an oven preheated to 140 °C for 24 h. The solid was washed six times with DMF and THF and then subjected to Soxhlet extraction with THF for 1 day to remove trapped guest molecules. The powder was collected and dried at 120 °C under vacuum overnight to produce GT-COF-3 in an isolated yield of 86%. Large-scale synthesis of GT-COF-3 TPB-BPTA-COF (800 mg) and TCNE (800 mg) were placed in a 50-mL Schlenk tube, with spatial separation maintained to prevent the two from directly contacting each other (e.g., by holding TCNE in a smaller tube sealed at one end). The Schlenk tube was degassed and then placed in an oven preheated to 140 °C for 24 h. The solid was washed six times with DMF and THF, and was then subjected to Soxhlet extraction with THF as solvent for 1 day to remove trapped guest molecules. The powder was collected and dried at 120 °C under vacuum overnight to produce GT-COF-3 in an isolated yield of 80%. Methods 1H and 13C NMR spectra were recorded on a Bruker AVANCE HD III 500M NMR spectrometer (Bruker Inc., Berlin, Germany). Fourier transform Infrared (FT-IR) spectra were recorded on an IFS 66V/S Fourier transform infrared spectrophotometer (Thermo Fisher Scientific Inc., Waltham, MA). Solid-state 13C cross polarization magic angle spinning nuclear magnetic resonance spectra (13C CPMAS NMR) were recorded on a JEOL JNM-ECA600 MHz, 3.2 mm rotor, magic angle spinning (MAS) of 20 kHz, recycle delay of 1 s (JEOL Ltd., Japan). UV–vis spectra were recorded on a Shimadzu UV-3600 spectrometer (Shimadzu Ltd., Japan). Elemental analysis was performed on an Elementar Vario EL elemental analyser (Elementar Analysensysteme GmbH, Germany). Thermogravimetric (TG) measurements were performed on a Rigaku Thermo plus EVO2 under N2, by heating to 800 °C at a rate of 5 °C min−1 (Rigaku Corporation, Japan). Field-emission scanning electron microscopy (FE-SEM) was performed on a Hitachi Regulus 8100 operating at an accelerating voltage of 5.0 kV (Hitachi Inc., Japan). High-resolution transmission electron microscopy (HR-TEM) images were obtained on a TEM JEOL 2100F with an acceleration voltage of 300 kV (JEOL Ltd., Japan). Electron spin resonance (ESR) spectra were measured on Bruker ELEXSYS-II E500 CW-ESR spectrometer (Bruker Inc., Berlin, Germany). Photothermal measurements were performed by using an 808-nm Fiber Coupled Laser (Model: MW-GX-808, Changchun Laser Optoelectronics Technology Co., Ltd., Changchun, China), and the temperature response of the samples was measured with an IR thermal camera (FLIR E4, FLIR Systems, Inc., United States). PXRD data were recorded on a Rigaku model RINT Ultima III diffractometer by depositing powder on glass substrate, from 2θ = 2° to 45° with 0.02° increment (Rigaku Corporation, Japan). Thermal conductivities were measured by Quantun Design PPMS-9 (Quantum Design, Inc., United States). XPS measurements were performed with Thermo Scientific ESCALAB XI+ (Thermo Fisher Scientific Inc., Waltham, MA). Power density of sun irradiation were controlled by using Neutral Density filter of Giai photonics Co., Ltd. (Shenzhen, China). Water contact angle were measured with betops DSA-X (betops scientific Co., Ltd., Guangzhou, China). Structural modelling The crystalline structures of COFs were determined using density-functional tight-binding (DFTB).25 The calculations were carried out with the DFTB+ program package version 17.1.26 DFTB25 is an approximate density functional theory (DFT) method based on the tight-binding approach and utilizes an optimized minimal linear combination of atomic orbitals (LCAO) Slater-type all-valence basis set in combination with a two-center approximation for Hamiltonian matrix elements. The Coulombic interaction between partial atomic charges was determined using the self-consistent charge (SCC) formalism. The lattice dimensions were optimized simultaneously with the geometry. Standard DFTB parameters for X–Y element pair (X, Y = C, H, O, and N) interactions were employed from the 3ob set.27–30 Accelrys Materials Studio 7.0 (Accelrys Software Inc., United States) was employed to build inputting files for DFTB simulation and visualize simulating results. All simulation works were performed using the computing resources at the National Supercomputing Center in Shenzhen. The highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) levels were calculated by using DFT calculation, which was carried out using the Gaussian 09 (version D.01) package on a PowerLeader cluster. The ground-state geometry was fully optimized using DFT with a B3LYP hybrid functional at the basis set level of 6–31G(d, p). Gas sorption measurements N2 and CO2 sorption measurements were performed on BELSORP-max (Bel Japan, Inc., Japan) automated volumetric sorption analysers. The desired temperature (77 and 195 K) was controlled by liquid N2 and a mixture of dry ice and isopropanol, respectively. Magnetic measurements Magnetic measurements were carried out on a Quantum Design MPMS 3 SQUID Magnetometer (Quantum Design, Inc., United States). Powder samples with a weight of 20 mg were sealed in a plastic capsule. The magnetic susceptibility was measured in the temperature range of 2–300 K with an applied field of 1000 Oe. Then the data were corrected for the diamagnetic contribution from sample holders and sample themselves using tabulated constants. The high magnetic field at of M(H) at 2 K curve was fitted using the following equation: M = F + A X where M is the magnetic moment per gram, F is the paramagnetic component (emu g−1), A is the diamagnetic background, and X is the applied magnetic field. The diamagnetic background was estimated based on the slope of M(H) at high magnetic field (H > 2 T). The obtained diamagnetic susceptibility M/H for GT-COF-3 was −6.53 × 10−7 emu Oe−1 g−1, which was a reasonable value for typical diamagnetism. Fabrication of photothermal devices 10–30 mg of samples were ground carefully and then ultrasonically dispersed in 10 mL of THF. The COF-loaded polyurethane (PU) foams were obtained by dropping the resulting suspensions onto circular and porous PU foams with diameters of 2 cm and drying under 40 °C under vacuum. Solar steam generation experiments The COF-loaded PU foams were put on a quartz beaker filled with water. The sunlight, generated by a solar simulator with an optical filter for the standard AM 1.5 G spectrum (CEL-S500/350/150), irradiated the sample under specific optical concentrations. The weight loss of water was measured by an electronic mass balance and the temperature over the process was recorded by an IR thermal camera. Calculation of the efficiency for solar to vapor generation The efficiency η of solar energy in photothermal-assisted water evaporation was calculated with the following formula31,32: η = m h LV / C opt P 0 where m refers to the mass flux (evaporation rate) of water, hLV refers to the total liquid-vapor phase-change enthalpy [i.e., the sensible heat and the enthalpy of vaporization (hLV = Q + Δℎvap)], Q is the energy provided to heat the system from the initial temperature T0 to a final temperature T; Δℎvap is the latent heat of vaporization of water; P0 is the nominal solar irradiation value of 1 kW m−2; and Copt represents the optical concentration. The schematic for the vaporization enthalpy of the vapor was as follows: Q = C liquid × ( T − T 0 ) Δ h vap = Q 1 + Δ h 100 + Q 2 Q 1 = C liquid × ( 100 − T ) Q 2 = C vapor × ( T − 100 ) In this work, Cliquid, the specific heat capacity of liquid water is a constant of 4.18 J g−1 °C−1. Cvapor, the specific heat capacity of water vaper is a constant of 1.865 J g−1 °C−1. Δℎ100 is the latent heat of vaporization of water at 100 °C, taken to be 2260 kJ kg−1. For example, the surface temperature of GT-COF-3 loaded PU (20 mg) was 43.6 °C during the evaporation process, therefore T is 43.6 °C. According to the above formulas, Q = C liquid × ( T − T 0 ) = 4.18 × ( 43.6 − 20.6 ) = 96.14 kJ kg − 1 Δ h vap = Q 1 + Δ h 100 + Q 2 = 4.18 × ( 100 − 43.6 ) + 2260 + 1.865 × ( 43.6 − 100 ) = 2390.566 kJ kg − 1 Δ h LV = Q + Δ h vap = 96.14 + 2390.566 = 2486.706 kJ kg − 1 m = 1.314 kg m − 2 h − 1 P 0 = 1 kW m − 2 C opt = 1 As a result, evaporation efficiency η = mhLV/CoptP0 = 90.7% when the latent heat of water vaporization at 43.6 °C (2390.566 kJ kg−1) is used in calculation. By the way, in this system, the solar evaporation was applied at temperatures above the environmental temperature, thus it was unnecessary to deduct the dark evaporation (<0.001 kg m−2 h−1). Desalination of seawater The real seawater sample (from the South Sea, China) was used for desalination by our system. The concentrations of all the five primary ions (Na+, Mg2+, Ca2+, K+, and Cl−) originally present in the sea water were examined by inductively coupled plasma optical emission spectroscopy (ICP-OES; Agilent 5110) before and after desalination. Then, the impact of ion concentrations on the efficiency, water evaporation rate, and photostability were evaluated. Long-term durability We carried out the long-term stability tests to check the durability in water evaporation. The cycle performance of COF-loaded PU evaporation system under fixed optical illumination (1 sun) was investigated under air for a continuous 2 h as one cycle (total 12 cycles). The mass change was recorded every 5 min. During the water evaporation process, the temperature of the surface of COF-loaded PU foam was monitored by an IR camera to study the photostability of the COF-loaded PU foam. Results and Discussion We chose an established imine-linked COF, TPB-BPTA-COF, as a platform to anchor the radical side chains because of its superior crystallinity, mesopores with high Brunauer–Emmett–Teller (BET) surface area, chemical robustness, and facile synthesis.33 We employed a classic type of radical generator, para-quinodimethanes, which has a typical closed-shell quinoidal and an open-shell radical resonance structure. The cyanovinyl decorated COF, termed GT-COF-3, was synthesized via a [2+2] CA–RE reaction of TCNE with the ethynyl groups suspended on the TPB-BPTA-COF (Figures 1a–1c and Supporting Information Figure S1).34 GT-COF-3 was thus transformed to radical COF by the structural resonance of carbonitrile-equipped buta-1,3-dienes and their radicals. Notably, the synthesis of TPB-BPTA-COF and GT-COF-3 was high-throughput with good yields: more than 1 g of COFs could be obtained from one batch of synthesis, compatible with large-scale production. We also synthesized a cyanovinyl quinoidal molecular analog 1 via a similar CA–RE reaction to the radical in such of quinoidal ( Supporting Information The of GT-COF-3 was characterized by various methods ( Supporting Information GT-COF-3 an of ethynyl at and an of at in the IR spectrum ( Supporting Information Figure and Solid-state 13C NMR of GT-COF-3 the presence of a to the at with the of the to the ethynyl at and ( Supporting Information Figure and Elemental analysis performed on the GT-COF-3 was in good with the ( Supporting Information XPS that the of to groups was ( Supporting Information Figure and which is to the one and thus the high yield of the CA–RE reaction and of six cyanovinyl groups one Figure 1 Synthesis and structures of the radical The of CA–RE reaction between TCNE and ethynyl Synthesis of TPB-BPTA-COF and GT-COF-3 reaction and [2+2] CA–RE respectively. The of the of GT-COF-3 and its resonance structure. of TPB-BPTA-COF and GT-COF-3 Download figure Download PowerPoint The crystallinity of the COFs was characterized by TPB-BPTA-COF the most at with several at and and were to the and the other GT-COF-3 the at and were to the of and We = stacking for the two COFs by using their optimized structures (Figures and The two COFs a of with = = and = the of were a = = = for TPB-BPTA-COF, and a = = = for GT-COF-3, ( Supporting Information and Notably, the PXRD results with the simulation that the lattice structures of GT-COF-3 in the postsynthetic process, the crystallinity in GT-COF-3 was because of the and of the in the Figure 2 and of the radical PXRD of TPB-BPTA-COF results in stacking in and GT-COF-3 results in and stacking in of the and side of layers of TPB-BPTA-COF C, H, of the and side of layers of GT-COF-3 C, H, of TPB-BPTA-COF and GT-COF-3 and open and absorption spectra of TPB-BPTA-COF and GT-COF-3 The of TPB-BPTA-COF and Download figure Download PowerPoint of the pore GT-COF-3 not N2 ( Supporting Information Figure of TPB-BPTA-COF measured at 195 K a type sorption with at a low pressure of by a at a of materials In GT-COF-3 a type with at a low pressure of 0.1 and increment at a high pressure of > that postsynthesis has GT-COF-3 to a and Supporting Information Figure GT-COF-3 surface of g−1 to that of TPB-BPTA-COF g−1), of the of channels by the decorated side To the stability of the radical COFs, we dispersed for 1 in water and GT-COF-3 weight loss in in water ( Supporting Information Figure The in PXRD after being in water for one and that GT-COF-3 its crystalline ( Supporting Information Figure The surface were and g−1 for GT-COF-3 for 1 in water at and °C, ( Supporting Information Figure are to that of the COFs. All results that the radical COF outstanding water a for photothermal such as solar-driven water evaporation. TPB-BPTA-COF a absorption from 250 to with a at as by spectroscopy TPB-BPTA-COF was in In GT-COF-3 and extended absorption spectra from 250 to 1400 GT-COF-3 was the the optical of TPB-BPTA-COF and GT-COF-3 were estimated to be and ( Supporting Information Figure DFT calculations of the COF a of and a of for TPB-BPTA-COF, to a of ( Supporting Information Figure By GT-COF-3 simultaneously of and of to a of The and from the radical of interactions between the framework and the and The low of GT-COF-3 provided more to radicals and thus of radical To the feature of radical in the COFs, we measured the COF samples in sealed quartz with TPB-BPTA-COF a with = from or groups at the By GT-COF-3 an at = which that the radical generated also possesses a spin of As a the molecular analog 1 an to that of GT-COF-3 ( Supporting Information Figure which that the spin in GT-COF-3 from their extended crystalline measurements from to K that the in GT-COF-3 as the increment of temperatures (Figures and Supporting Information Figure of spin a feature of radicals with The temperature of the spin susceptibility determined by the that the spin susceptibility as the of temperature ( Supporting Information Figure constant for GT-COF-3 above 120 K ( Supporting Information Figure the is by the interaction between in

Topics & Concepts