Metalloporphyrin and Ionic Liquid-Functionalized Covalent Organic Frameworks for Catalytic CO2Cycloaddition via Visible-Light-Induced Photothermal Conversion

Induced Photothermal Conversion

Article

Metalloporphyrin and Ionic Liquid-Functionalized Covalent Organic

Frameworks for Catalytic CO Cycloaddition via Visible-Light-

Luo-Gang Ding, Bing-Jian Yao,* Wen-Xiu Wu, Zhi-Gao Yu, Xiao-Yu Wang, Jing-Lan Kan,

and Yu-Bin Dong *

Cite This: https://doi.org/10.1021/acs.inorgchem.1c01975

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sı Supporting Information

ABSTRACT: We report the construction of a porphyrin and

imidazolium-ionic liquid (IL)-decorated and quinoline-linked

covalent organic framework (COF, abbreviated as COF-P1-1)

via a three-component one-pot Povarov reaction. After post-

synthetic metallization of COF-P1-1 with Co(II) ions, the

metallized COF-PI-2 is generated. COF-PI-2 is chemically stable

and displays highly selective CO adsorption and good visible-

light-induced photothermal conversion ability (ΔT = 26 °C).

Furthermore, the coexistence of Co(II)−porphyrin and imidazo-

lium-IL within COF-PI-2 has guaranteed its highly eﬃcient

activity for CO cycloaddition. Of note, the needed thermal energy

for the reactions is derived from the photothermal conversion of

the Co(II)−porphyrin COF upon visible-light irradiation. More

importantly, the CO cycloaddition herein is a “window ledge” reaction, and it can proceed smoothly upon natural sunlight

irradiation. In addition, a scaled-up CO cycloaddition can be readily achieved using a COF-PI-2@chitosan aerogel-based ﬁxed-bed

model reactor. Our research provides a new avenue for COF-based greenhouse gas disposal in an eco-friendly and energy- and

source-saving way.

INTRODUCTION

with cocatalysts, sometimes harsh reaction conditions (>100

■

21,22

C, >1.0 MPa), and energy consumption.

To meet the

Carbon dioxide (CO ), a main gas for the greenhouse eﬀect,

multifaceted requirements of good chemical stability, high

activity, simpliﬁed product-catalyst separation, energy and

source saving, the design and synthesis of new types of

causes a series of environmental issues. Faced with an

escalating level of atmospheric CO concentration, its capture

and storage/sequestration (CCS) have recently received

intense attention. Compared with the CCS, the development

of new types of eﬃcient CO₂adsorbents that can

heterogeneous catalysts for CO cycloaddition are highly

imperative.

synchronously convert CO into value-added chemicals has

As an emerging class of porous organic crystalline materials,

covalent organic frameworks (COFs) have recently drawn

intense attention due to their versatile potential applications in

been demonstrated to be a more useful way for addressing

−5

CO emissions.

In this context, chemical conversion of the

24−31

32,33

34,35

ﬁxed CO within porous materials into cyclic carbonates,

catalysis,

nanomedicine.

gas adsorption/separation,

sensing,

and

36−38

which are an important class of ﬁve-membered chemicals, to

valuable industrial products via cycloaddition with epoxides

has emerged as an attractive approach due to its hundred

Unlike two-component polymerization,

we and others recently developed a new multicomponent one-

pot polymerization methodology, which can be an alternative

,6,7

percent atomic utilization rate.

So far, various solid materials, including polymeric ionic

way to access multifunctional COFs with new connecting

24,27,39,40

linkages.

In addition, the multicomponent one-pot

−11

13−15

liquids (IL),

zeolites, silica-supported salts,

micro-

and metal−organic frame-

have been used as the heterogenous catalysts to

6,17

porous organic polymers,

8−20

Received: June 30, 2021

works

conduct the catalytic CO -based cyclic carbonates, and some

of them indeed exhibit good performance in both selective

CO adsorption and its catalytic chemical conversion. Despite

these unquestionable advancements though, the reported

catalysts might still suﬀer from complicated catalytic systems

XXXX American Chemical Society

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

Article

Scheme 1. (a) Synthesis of COF-PI-2 and Its Catalytic CO Cycloaddition with Epoxides; (b) Synthesis of a Model Compound

Based on a Three-Component One-Pot Povarov Reaction

polymerization aﬀords a unique opportunity to simultaneously

introduce diﬀerent functional groups into COF frameworks.

Inspired by this, we prepared a quinoline-linked and porphyrin

and IL-decorated COF (termed as COF-PI-1) by the three-

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

Article

component one-pot Povarov reaction using amino-substituted

porphyrin 5,10,15,20-tetrakis(4-aminophenyl) porphyrin

Synthesis of the Model Compound. A mixture of benzaldehyde

Ba) (170 mg, 1.6 mmol), aniline (149 mg, 1.6 mmol), Bim-Br (398

(

mg, 1.6 mmol), BF ·OEt (20 μL, 0.3 mmol), 2,3-dicyano-5,6-

(

Tph), imidazolium-IL-attached styrene 3-methyl-1-(4-vinyl-

dichloroben-quinone (DDQ) (40 mg, 0.3 mmol), and acetic acid (6

benzyl)-benzimidazolium bromide (Bim-Br), and 2,5-dihy-

droxyterephthalaldehyde (Dha) as monomers. After metal-

M, 2 mL) in o-dichlorobenzene (o-DCB)/n-butanol (n-BuOH) (1/1,

0 mL) was heated at 120 °C for 24 h. The solvent was removed

lization of the porphyrin entity by Co(OAc) in COF-PI-1 via

under reduced pressure. The crude product was puriﬁed by column

chromatography on silica gel (CH Cl /MeOH, 10/1, v/v) to aﬀord

post-synthetic modiﬁcation, COF-PI-2 with both metal-

loporphyrin and imidazolium-IL species was obtained.

As shown in Scheme 1a, the major advantage of COF-PI-2

is that the metalloporphyrin (Co(II)−Tph) and imidazolium-

the model compound as a brown-yellow solid in 91% yield (620 mg).

H NMR (400 MHz, DMSO-d ): δ 9.20 (s, 1H), 8.44 (s, 1H), 8.04

(d, 2H), 7.94 (d, 2H), 7.80 (d, 2H), 7.68 (d, 2H), 7.60 (d, 3H), 7.51

19,20,41,42

IL entities, which are both CO -philic catalysts,

are

(s, 4H), 5.79 (s, 2H), 4.11 (s, 3H). C { H} NMR (100 MHz,

DMSO-d ): δ 156.76, 148.47, 143.48, 143.07, 137.97, 136.39, 131.78,

linked together via chemically stable quinoline linkage.

30.75, 129.42, 128.54, 127.09, 127.01, 124.07, 119.49, 115.75,

Moreover, it shows a highly selective CO adsorption and

14.23, 114.17, 49.94, 33.85. HRMS (ESI) m/z: [M]⁺calcd for

excellent catalytic conversion by cycloaddition with epoxides

under solvent-free conditions without any co-catalysts. Owing

to the existence of photothermal Co(II)−porphyrin in COF-

C H N , 426.1965; found, 426.1924.

Synthesis of COF-PI-1. A mixture of Dha (13.3 mg, 0.08 mmol),

Tph (27 mg, 0.04 mmol), Bim-Br (39.8 mg, 0.16 mmol), BF ·OEt

5,43,44

PI-2,

the endothermic CO cycloaddition herein can be

(2.0 μL, 0.03 mmol), DDQ (4.0 mg, 0.03 mmol), and acetic acid (6

M, 0.2 mL) in o-DCB/n-BuOH (1/1, 2 mL) was heated at 120 °C for

triggered upon visible-light (including natural sunlight)

irradiation via photothermal conversion. Remarkably, the

processable COF-PI-2@chitosan aerogel was readily shaped

into a simpliﬁed ﬁxed-bed model reactor via a facile templated

freeze-drying procedure, and a scaled-up recyclable CO₂

cycloaddition was successfully realized under photothermal

conditions with good reusability.

7 days in a N atmosphere. After cooling to room temperature, the

solids were collected by centrifugation and successively washed with

DMF, THF, and ethanol and then dried in vacuum (100 °C for 24 h)

to aﬀord COF-PI-1 as a dark red crystalline solid in 81% yield (31.2

−

mg). IR (KBr, cm ): 3308 (w), 1589 (s), 1531 (m), 1477 (s), 1331

m), 1231 (m), 1178 (s), 996 (w), 793 (m). Elemental Anal. (%)

Calcd for (C H N O Br ) : C, 68.76; N, 10.03; H, 4.03. Found

(

2 n

(

%): C, 69.54; N, 10.21; H, 4.04. Br content was 12.89 wt % (calcd,

EXPERIMENTAL SECTION

■

14.33 wt %) based on ICP measurement.

Materials and Instruments. All the reagents and chemicals were

purchased from commercial sources without further puriﬁcation.

Synthesis of COF-PI-2. A mixture of COF-PI-1 (10 mg) and

cobalt(II) acetate (100 mg) was stirred in DMF (10 mL) for 24 h at

80 °C under a N₂atmosphere. The solids were collected by

centrifugation and sequentially washed with DMF and acetone and

then dried in vacuum at 80 °C overnight to aﬀord COF-PI-2 (9.5 mg,

92% yield). FT-IR (KBr, cm ): 3308 (m), 1589 (s), 1531 (m), 1464

(w), 1304 (w), 1159 (m), 996 (w), 800 (m). The Co and Br amounts

in COF-PI-2 were determined as 2.55 wt % (calcd, 2.58 wt %) and

12.57 wt % (calcd, 13.97 wt %), respectively.

Fabrication of COF-PI-2@Chitosan Aerogel-Based Cup-like

Reactor. 1.62 g of crystalline COF-PI-2, 300 glass beads (d = 2 mm),

and 500 μL of 1,4-butanediol diglycidyl ether were added into acidic

aqueous solution of chitosan (0.41 g of chitosan, 0.12 mL of HOAc,

46,47

Dha, Tph,

and Bim-Br were synthesized according to the

reported procedures. All the characterization data for the known

compounds were well consistent with the reported results (Schemes

S1−S3 and Figures S1−S18 in the Supporting Information for

details). In our experiments, there are no new, unexpected, and/or

−

signiﬁcant hazards or risks. H-NMR, C-NMR, and solid-state

CP-MAS NMR spectra were conducted on a Bruker Avance-400 HD

and an Avance II 400 spectrometers, respectively. FT-IR spectroscopy

was employed using the Bruker Alpha FT-IR spectrometer in the

−

range of 400−4000 cm . High-resolution mass spectrometry

(

HRMS) was performed on a Bruker maXis ultra-high-resolution

mass spectrometer. Inductively coupled plasma (ICP) measurements

were performed on IRIS Intrepid (II) XSP and Nu AttoM. Scanning

electron microscopy (SEM) was conducted on a Gemini Zeiss

SUPRA scanning electron microscope equipped with an energy-

dispersive X-ray (EDX) detector. Transmission electron microscopy

and 10 mL of H O) with ultrasonic shaking to aﬀord a homogeneous

suspension. The obtained solution was immediately transferred into

the “split-ﬂask” quartz mold and allowed to stand for ca. 12 h until a

robust hydrogel was formed. After freezing at −18 °C, the frozen

sample was freeze-dried at −50 °C for 24 h in a freeze-dryer to form

the dry COF-PI-2@chitosan aerogel monolith with 80 wt % of COF-

PI-2 loading. After thorough washing with ethanol to remove residual

acetic acid, the obtained COF-PI-2@chitosan aerogel-based cuplike

reactor was applied to catalysis.

(

TEM) images were acquired using a JEOL JEM-1400plus (120 kV).

Powder X-ray diﬀraction (PXRD) patterns were obtained on a D8

Advance X-ray powder diﬀractometer using Cu Kα radiation (λ =

1.5405 Å). Elemental analysis was collected on a Flash EA 1112. Gas

adsorption/desorption isotherms were performed on ASAP 2020/

TriStar 3000 (Micromeritics) at 77 and 298 K. Selective CO₂

adsorption is expressed by the Henry adsorption selectivity of CO₂/

Photothermal Behavior of COF-PI-2. The suspension of COF-

PI-2 in epibromohydrin with diﬀerent mole fractions (0.25 = 1.0 mol

% based on imidazolium-IL species) was placed upon a 500 W xenon

lamp (λ > 400 nm), where the distance between the light source and

the reaction bottle was ﬁxed at 15 cm, and the power density

measured by a power density meter was 80 mW cm . The real-time

temperature is measured and captured by a thermocouple

thermometer and thermal imager, respectively.

N according to the direct ﬁtting of the gas adsorption isotherm

within the low-pressure Henry region. Thermogravimetric analysis

−

(

TGA) was performed on a TA Instrument Q5 synchronous

thermogravimetric analyzer between 25 and 800 °C with a ﬂow of

N₂at 60 °C min⁻and a heating rate of 10 °C min . X-ray

photoelectron spectroscopy (XPS) data were obtained using a 300 W

Al Kα radiation PHI-5000 Versaprobe II (VP-II) electronic

spectrometer. UV−vis spectroscopy was performed on a TU-

−1

Catalytic Cycloaddition of CO with Epoxides over COF-PI-

2. General Procedure. Typically, a mixture of epoxide (11.6 mmol)

and COF-PI-2 (1.0 mol % imidazolium-IL equiv) was stirred under a

solvent-free condition and with 500 W xenon lamp (λ > 400 nm, 80

900Beijing PuXi. The contact angle measurement was conducted

−

on a OCA15 contact angle analyzer (DataPhysics, Germany). The

photothermal eﬀect was evaluated by a Ulead K-type temperature

measuring instrument equipped with a thermocouple. Photo-induced

photothermal catalysis was performed with a xenon lamp (λ > 400

mW cm , 15 cm away from the reaction vessel) irradiation for 24 h

under 1 atm CO without an external heat source. The thermocouple

was used to measure the real-time temperature. After the reaction, the

catalyst was recovered by centrifugation, completely rinsed with

acetone, and dried under vacuum at 80 °C overnight for the next

catalytic cycle performed under the same conditions. The crude

products were puriﬁed via column chromatography in silica gel

−

nm, 500 W, 80 mW cm ). The real optical power density was

measured using a Thorlabs PM100D digital display optical power

meter.

Inorg. Chem. XXXX, XXX, XXX−XXX

isotherms of COF-PI-1 and COF-PI-2 . (d) TGA curves of COF-PI-1 and COF-PI-2 .

Article

Figure 1. (a) FT-IR spectra of COF-PI-1, COF-PI-2, and the monomers. (b) Simulated and measured PXRD patterns of COF-PI-1 and COF-PI-

: comparison between the experimental (red and green lines) and Pawley-reﬁned proﬁle (black dots), the simulated pattern for eclipsed (AA)

stacking mode (purple line), and the reﬁnement diﬀerence (blue line). Inset: top view of the structural model of COF-PI-1. (c) N adsorption

Figure 2. CO (a) and N (b) adsorption isotherms of COF-PI-1 and COF-PI-2 at 298 K, respectively.

(

eluent: CH Cl /PE = 5/1, v/v) and their structures were determined

Leaching Test. The solid catalyst of COF-PI-2 (1.0 mol %

imidazolium-IL equiv) was isolated from reaction solution by

centrifugation after 12 h. Then, the ﬁltrate was allowed to react for

an additional 12 h under the same reaction conditions. The samples

by H NMR and MS spectra.

For scaled-up model cycloaddition with the cuplike reactor,

epibromohydrin (60 mL, 630 mmol) was added into a split-ﬂask

equipped with COF-PI-2@chitosan aerogel (1.8 g, 0.5 mol %

imidazolium-IL equiv). The reaction was performed under a 500 W

xenon lamp (λ > 400 nm, 80 mW cm ) irradiation (monitored by H

NMR) under 1 atm CO without an external heat source. After the

reaction, the product was separated by dumping, and the crude

product was puriﬁed via column chromatography on silica gel (eluent:

CH Cl /PE = 5/1, v/v) and its structure was determined by H NMR

were taken every 3 h to detect the corresponding yield by H NMR.

−

RESULTS AND DISCUSSION

■

Synthesis and Characterization of COF-PI-1 and COF-

PI-2. Based on the model reaction among aniline, Ba, and Bim-

Br (Scheme 1b and Figures S19 −S21 ), the three-component

one-pot in situ polymerization of Dha, Tph, and Bim-Br in the

and MS spectra. The COF-PI-2@chitosan aerogel was washed with

acetone and dried in vacuum at 80 °C overnight for the next catalytic

cycle under the same reaction conditions.

presence of acetic acid, BF ·OEt , and DDQ under

3 2

solvothermal conditions (o-DCB/n-BuOH, 120 °C, 7 days)

Inorg. Chem. XXXX, XXX, XXX−XXX

(Scheme 1 a). Formation of the quinoline linkage was veriﬁed

Article

−

Figure 3. Photothermal behavior of COF-PI-2 in epibromohydrin (500 W xenon lamp, 80 mW cm , λ > 400 nm, 15 cm away from the reaction

system, the initial temperature is 25 °C). (a) Visible-light induced temperature-increase of epibromohydrin with diﬀerent amounts of COF-PI-2.

(

b) Temperature of the COF-PI-2-epibromohydrin system under continuous visible-light irradiation for 24 h (500 W xenon lamp, λ > 400 nm, 80

−

mW cm , 15 cm away from the reaction vessel).

Table 1. Optimization of COF-PI-2-Catalyzed CO₂

Cycloaddition with Epibromohydrin

by FT-IR and solid-state C-NMR spectroscopy. As shown in

Figure 1a, the typical N−H vibration peaks at 3352 and 3213

−

−1

cm in Tph and the CO vibration peak at 1669 cm in

Dha disappeared after polymerization. Meanwhile, new

characteristic peaks for CN groups at 1589 and 1531

−

cm demonstrated the formation of a quinolyl moiety in

COF-PI-1. In its solid-state C-MAS NMR spectrum, a

strong peak at ca. 156.9 ppm corresponding to the 2-quinolyl

carbon was clearly observed (Figure S22).

As revealed by the measured PXRD patterns, the obtained

COF-PI-1 was highly crystalline and displayed prominent

peaks at ca. 3.5, 4.9, 6.9, and 22.3 corresponding to (100),

110), (200), and (001) facets, respectively. The simulation of

its PXRD pattern with Materials Studio (Version 2018)

suggested that it possessed the most probable structure with

D eclipsed (AA) stacking, and the Pawley reﬁnement showed

a negligible diﬀerence between the simulated and experimental

PXRD patterns (Figure 1b). COF-PI-1 was assigned to the P₄

space group with optimized parameters a = b = 35.8 Å, c = 5.3

entry catalyst (mol %)

condition

25 °C/dark

40 °C/dark

t (h) yield (%)

2 (1 mol %)

2 (0.25 mol %)

2 (0.5 mol %)

1 (1 mol %)

2 (1 mol %)

51 °C/dark

visible-light irradiation

sunlight irradiation

(

Reaction conditions: 11.6 mmol of epibromohydrin, 1 atm of CO₂,

solvent-free, and visible-light irradiation (500 W xenon lamp, 80 mW

−

cm , λ > 400 nm, the initial temperature is 25 °C, and 15 cm away

from the reaction system). Isolated yield. Reaction conditions: 11.6

^Å^,^α⁼^β ⁼⁹ ⁰ ^°^,^γ ⁼⁹⁰^°^,^aⁿ^d^r^e^sⁱ^d^u^a^l^s^Rwp = 11.35% and R =

8.58% (Table S1 ). The porosity of COF-PI-1 was examined by

mmol of epibromohydrin, 1 atm of CO , solvent-free, and natural

sunlight irradiation for 24 h.

N adsorption−desorption measurements at 77 K. As shown in

Figure 1c, the N adsorption capacity and Brunauer−Emmett−

aﬀorded COF-PI-1 as brick red crystalline solids in 81% yield

Teller (BET) surface area of COF-PI-1 were determined as

−1

251.9 cm g and 420.6 m g , respectively. The average pore

Figure 4. COF-PI-2-catalyzed CO cycloaddition with epibromohydrin. (a) Reaction time examination (blue line) and leaching test (red line) for

CO cycloaddition with epibromohydrin catalyzed by COF-PI-2. Reaction conditions: solvent free, epibromohydrin (1.1 mL, 11.6 mmol), COF-

−2

PI-2 (1.0 mol % IL equiv), CO (1 atm), 500 W xenon lamp (λ > 400 nm, 80 mW cm ). (b) Catalytic cycles. (c) Corresponding PXRD patterns

after each catalytic cycle.

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

Article

Table 2. CO Cycloaddition with Diﬀerent Epoxides over COF-PI-2

Reaction conditions: 11.6 mmol of epoxy compounds, 1 atm of CO , solvent-free, COF-PI-2 (1 mol % IL equiv, 500 W xenon lamp, λ > 400 nm,

0 mW cm ). Isolated yield. The corresponding H NMR and MS spectra for the obtained cyclic carbonates are shown in Figures S38 −S45 .

−2

Scale-up experiment based on the cup-like reactor: epibromohydrin (630 mmol, 60 mL), CO (1 atm), aerogel (18.0 g, 0.5 mol % COF-PI-2

−

equiv), 500 W xenon lamp (λ > 400 nm, 80 mW cm ), and solvent-free.

size distribution was centered at ca. 1.0 nm based on Barrett−

Joyner−Halenda analysis (Figure S23 ), which is in good

agreement with that calculated from its crystal structure.

replaced by a single N 1s peak at 398.6 eV in COF-PI-2 after

metallization. Meanwhile, the other two peaks at 796.6 and

781.3 eV for Co 2p₁_/₂and Co 2p₃_/₂appeared. These results

deﬁnitely conﬁrmed that the Co(II) ions were successfully

trapped by the porphyrin in COF-PI-2. In addition, the N 1s

peak at 399.8 eV for the quinoline moiety in COF-PI-1

remained unchanged after metallization, indicating that Co(II)

Upon reaction of COF-PI-1 with Co(OAc) in DMF at 80

C for 24 h, COF-PI-2 was generated (Scheme 1a). As

determined by the ICP measurement, the metallization of

porphyrin in COF-PI-2 is quantitative (measured 2.55 wt %,

calculated 2.58 wt %). As shown in the XPS spectra (Figure

S24 and Table S2), the double peaks at 400.0 and 398.1 eV for

N 1s in COF-PI-1 associated with the free porphyrin were

50,51

ions did not coordinate to the quinoline group.

After

metallization, the N adsorption capacity and BET surface area

−1

of COF-PI-2 slightly decreased to 247.8 cm g and 409.1 m

Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Figure 5. (a) Top photographic view of the cup-like reactor. (b) SEM image of the COF-PI-2@chitosan aerogel (COF-PI-2, 80 wt %). (c) PXRD

patterns of COF-PI-2, COF-PI-2@chitosan aerogel, and chitosan aerogel. (d) N adsorption isotherms (at 77 K) of COF-PI-2, COF-PI-2@

chitosan aerogel, and pure chitosan aerogel.

−

g , respectively (Figure 1c). Moreover, the measured amount

ratio of the initial slopes in the low-pressure Henry region of

−

16,20

of Br (12.57 wt %) was in good agreement with that of the

the single-component gas adsorption isotherms.

Accord-

calculated one (12.61 wt %), indicating that no anion-exchange

of Br by acetate occurred during the metallization process. As

ingly, the adsorptive selectivities of COF-PI-1 and COF-PI-2

−

for the equimolar CO /N mixture was up to 39.1 and 46.7,

indicated in Figure 1b, the crystallinity and structural integrity

of COF-PI-1 was well maintained after post-synthetic

metallization.

respectively (Figure S29 ). The higher selective CO adsorption

of COF-PI-2 for CO was logically ascribed to the coexistence

of the embedded CO -philic Lewis acid (metalloporphyrin)

19,20,41,42

The SEM images showed that both COF-PI-1 and COF-PI-

and imidazolium-IL sites within its framework.

were obtained as rod-like nanoparticles, and no diﬀerent

Photothermal Behavior of COF-PI-2. As mentioned

morphology was observed, implying that they were obtained in

a single phase (Figure S25 ). The TEM images further

evidenced their high crystalline nature (Figure S26 ). In

addition, the EDX spectra (EDX-mapping) of COF-PI-1 and

COF-PI-2 indicated that the elements homogeneously

dispersed in the COF matrix (Figure S27 ). TGA revealed

that both COF-PI-1 and COF-PI-2 were intact up to ca. 200

above, the metalloporphyrin- and imidazolium-IL-containing

COF-PI-2 displayed higher selective CO adsorption, so we

decided to examine its catalytic activity toward the CO₂

cycloaddition with epoxide under solvent-free conditions. As

we know, metalloporphyrin-containing materials usually

possess visible-light-induced photothermal conversion behav-

42,52

ior,

so we wondered if the CO cycloaddition, which is a

C, suggesting that they possess good thermostability (Figure

typical thermally driven reaction, could be triggered by the

photothermal conversion upon irradiation with visible-light.

For this, the photothermal conversion behavior of COF-PI-2

was ﬁrst evaluated in epibromohydrin based on its adsorption

spectrum (Figure S30). As shown in Figure 3a, when COF-PI-

d). In addition, COF-PI-2 is chemically stable, and it can

tolerate various organic solvents (DMSO, DMF, MeCN,

CH Cl , THF, and acetone) as well as HCl (2 M), NaOH (2

M), and NaBH (1 M) aqueous solutions (Figure S28).

Selective CO Adsorption. Considering the high density

in epibromohydrin (0.25, 0.5, 1.0 mol %) was irradiated with

of porphyrin and imidazolium-IL species in COF-PI-1 and

COF-PI-2, their selective CO adsorption over N under

−

visible-light (500 W xenon lamp, λ > 400 nm, 80 mW cm )

for 80 min, the equilibrium temperatures of 39.8, 46.1, and

ambient conditions was expected. As illustrated in Figure 2a,b,

51.0 °C can be achieved from 25 °C. In contrast, only an 8.5

COF-PI-1 and COF-PI-2 exhibited the CO uptake amounts

−1

C temperature increase was observed for epibromohydrin

up to 30.98 and 33.30 cm g at 298 K under 1 atm;

−1

meanwhile, only a small uptake amount of N (2.19 cm g for

without COF-PI-2 under the same conditions. As shown in

Figure 3b, the temperature of epibromohydrin with 1.0 mol %

of COF-PI-2 could be readily maintained in a range of 50−51

°C for at least 24 h upon visible-light irradiation, implying that

it could be used for the photothermal catalytic application.

−1

COF-PI-1 and 2.30 cm g for COF-PI-2) by them was

observed under the same conditions. To assess the selectivity

of CO over N , the ideal adsorption selectivity toward an

equimolar binary mixture of CO /N was calculated from the

Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Figure 6. (a) Photograph of the cup-like reactor based on the COF-PI-2@chitosan aerogel. (b) Reaction monitoring epibromohydrin (630 mmol,

−

0 mL), CO (1 atm), aerogel (18.0 g, 0.5 mol % COF-PI-2 equiv), 500 W xenon lamp (λ > 400 nm, 80 mW cm ), solvent-free). (c) Catalytic

cycles. After each run, the reaction solution was poured out, and the cup-like aerogel was completely washed with ethanol and dried in vacuum. (d)

PXRD patterns of the COF-PI-2@chitosan aerogel after each catalytic run.

CO Cycloaddition Catalyzed over COF-PI-2. Based on

1.0 mol % COF-PI-2, solvent-free, and 24 h under visible-light

irradiation (500 W xenon lamp, λ > 400 nm, 80 mW cm ).

−

the above observation, the catalytic CO cycloaddition over

COF-PI-2 was then evaluated. Herein, epibromohydrin was

employed as the model substrate in the screening of CO₂

cycloaddition parameters over COF-PI-2. As shown in Table

The eﬀective utilization of sunlight, the most plentiful and

clean energy on the surface of the earth, to drive CO chemical

transformation is highly signiﬁcant. Much to our delight, the

^C^O2 cycloaddition herein could smoothly proceed under

, the desired product was obtained in yields of 13 and 68% at

5 and 40 °C in the dark over 1.0 mol % of COF-PI-2 after 24

−

natural sunlight (measured power density of 10−55 mW cm

and reaction solution temperature of 25 −48 °C during daytime

irradiation from 7:00 am to 7:00 pm, Figures S31 −S33), and

the cycloaddition reaction yield was up to 90% yield after 24 h

of sunlight irradiation (Table 1, entry 8). This “window ledge”

reaction undoubtedly provides a strong foundation for the

future development of COF-based and solar-powered organic

h (Table 1, entries 1 and 2). A quantitative yield (99%) was

obtained when the reaction was carried out at 51 °C without

any additives, indicating the positive correlation between yield

and temperature (Table 1, entry 3). Remarkably, COF-PI-2

displayed the same catalytic activity under visible-light

irradiation (500 W xenon lamp, λ > 400 nm, 80 mW cm ),

wherein the measured system temperature was up to 51.3 °C

and a 99% yield was detected within 24 h (Table 1, entry 4). In

addition, when the reaction was performed with a lower

catalyst loading, 0.25 and 0.5 mol % instead of 1.0 mol %, the

product was obtained in lower 39 and 76% yields, respectively

−

reactions. To our knowledge, COF-PI-2 is the ﬁrst example

of thermally driven CO cycloaddition via visible-light-induced

photothermal conversion on a COF-catalyst, and it exhibits

comparable catalytic performance to the reported COF-

catalysts (Table S3 ).

The hot leaching test demonstrated that COF-PI-2 is a

typical heterogeneous catalyst (Figure 4a), and the yield for

expected cyclocarbonate was still up to 97.5% even after ﬁve

catalytic cycles (Figure 4b). The crystallinity and structural

integrity of COF-PI-2 were well maintained after multiple

catalytic runs (Figure 4c), indicating the robust nature of the

quinoline linkage. The Br and Co amounts after ﬁve catalytic

runs were determined to be 12.51 and 2.52 wt % by ICP,

which are consistent with those of as-synthesized COF-PI-2

(12.57 and 2.55 wt %). As depicted by XPS, no change of

valence state of the cobalt(II) ion occurred after multiple

catalytic cycles (Figure S34). In addition, the SEM, TEM, and

(Table 1, entries 5 and 6), which clearly resulted from the

lower photothermal (Figure 3a) and catalytic sites’ loading. In

contrast, for the reaction catalyzed over COF-PI-1 with only

imidazolium-IL under the same visible-light irradiation

(

measured system temperature, 49 °C), an 83% yield was

obtained within 24 h (Table 1, entry 7), which evidenced that

the CO cycloaddition herein was activated by both metal-

loporphyrin and imidazolium-IL species within COF-PI-2.

The turnover number and turnover frequency for the model

−

reaction over COF-PI-2 are 98.5 and 4.1 h , respectively.

Thus, the best reaction conditions herein were determined as

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

The Supporting Information is available free of charge at

Article

SEM−EDX mapping revealed that no changes in morphology,

particle size, crystallinity, and chemical composition occurred

after multiple catalytic cycles (Figures S35 and S36). Thus, the

COF-PI-2 described herein is an ideal multifunctional

well and the desired product was isolated in 93% yield in 60 h

(Figure 6b, Table 2, entry 8, and Figure S45). After the

reaction, the product−catalyst separation was readily achieved

by simply decanting, and the cup-like reactor was directly used

for the next catalytic cycle after washing with acetone and

vacuum drying. The cup-like reactor was robust and could be

reused for at least ﬁve times without loss of its catalytic activity

(yield ≥ 91%, Figure 6c). Additionally, the PXRD patterns

showed that the crystallinity of COF-PI-2 was well maintained

during the reusable catalytic process (Figure 6d). Thus, the

ﬁxed-bed model herein is highly eﬃcient, versatile, maneuver-

able toward organic catalytic conversion, and it eﬀectively

overcame the issues of catalyst regeneration and product

separation associated with the reactions catalyzed by particle

COF catalysts.

platform for both CO selective adsorption and chemical

conversion. Accordingly, a possible mechanism was proposed

for the CO cycloaddition catalyzed by COF-PI-2 (Figure

4,55

S37 ).

In addition, the visible-light-induced thermally driven CO₂

cycloaddition can be readily extended to various other

substrates with desirable performance under the optimized

conditions. For epibromohydrin, epichlorohydrin, allyl glycid-

yl, and epoxy octane, the corresponding products were

obtained in 99, 99, 96, and 91% yields, respectively (Table

, entries 1−4, and Figures S38 −S41). In case of the long-

chain substituted 1,2-epoxyoctadecane, however, the reaction

gave a very low 7% yield (Table 2, entry 5, and Figure S42),

which should result from its limited diﬀusion within the COF

framework. The reaction worked well for aryl-substituted

epoxy compounds, glycidyl phenyl ether, and styrene oxide,

giving moderate yields of 65 and 59% (Table 2, entries 6, 7 and

Figures S43 and S44), respectively.

CONCLUSIONS

■

In summary, a multifunctional COF equipped with metal-

loporphyrin and imidazolium-IL is successfully constructed by

a combined three-component one-pot Povarov reaction and

post-synthetic metallization approach. The obtained COF-PI-2

exhibits highly selective CO₂adsorption under ambient

conditions. Besides, it can be a recyclable catalyst to

Fabrication of the COF-based shapable setup is very

important to realize their practical applications, especially in

ⁱⁿ^d^u^s^t^r^y^.^F^o^r^a^c^hⁱ^e^vⁱⁿ^g^s^c^a^l^e^-^u^p^C^O2 cycloaddition, we

designed and fabricated a COF-PI-2@chitosan aerogel-

based cup-like reactor, which was used as a ﬁxed-bed model

to test its catalytic activity in a larger scale. Herein, we used

eco-friendly and low-cost chitosan to incorporate COF-PI-2

into the aerogel to achieve its molding. For enhancing its

robustness and photothermal conversion eﬃciency, cross-

linker 1,4-butanediol diglycidyl ether and glass beads were

added during the aerogel formation process templated by a

signiﬁcantly promote CO chemical transformation by cyclo-

addition with epoxides under visible-light irradiation via

photothermal conversion. What is particularly interesting is

that the reaction could eﬀectively proceed even under natural

sunlight irradiation, which displays a potential application in

solar-powered CO chemical conversion. More importantly,

the multifunctional COF can be shaped into a ﬁxed-bed model

reactor via incorporating with chitosan by a facile templated

freeze-drying approach, which allows a scale-up of CO₂

cycloaddition with high activity and excellent recyclability.

We believe that our research provides a new way for

constructing multifunctional COF-based catalysts as well as

16,25

split-ﬂask (Figure 5a).

As shown in Figure 5b, the COF-

PI-2 nanoﬁbers are homogeneously blended in the chitosan

phase and no detectable interface boundary was observed. The

PXRD pattern of the COF-PI-2@chitosan aerogel showed

that the COF-PI-2 structural integrity and crystallinity were

well maintained in the composite sponge-like aerogel (Figure

an eﬀective pathway for CO transformation and environ-

mental protection.

ASSOCIATED CONTENT

sı Supporting Information

https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c01975.

■

c). As the ice-template-generated macropores did not

signiﬁcantly contribute to the surface area, the COF-PI-2@

chitosan aerogel showed a decreased N adsorption capacity

−1

(

115.1 cm g ) and a lower BET speciﬁc surface area (101.1

−1

m g ) in comparison with the COF-PI-2 crystals. On the

other hand, the involved COF crystals largely enhanced the gas

capacity and BET speciﬁc surface area of the pure chitosan

Characterization of Dha, Tph, Bim-Br, model com-

pounds, COF-PI-1, COF-PI-2, and COF-PI-2@chito-

san; general catalytic CO₂cycloaddition product

characterization; and catalytic cycles and proposed

mechanism (PDF )

−1

aerogel (3.05 cm g and 8.1 m g ) (Figure 5d). The

wettability of epibromohydrin on the COF-PI-2@chitosan

aerogel was assessed by contact angle measurement, where the

rapid penetration of an epibromohydrin droplet into the

aerogel within 2 s indicated their desirable aﬃnity (Figure

S46 ). In addition, as revealed by the TGA trace, COF-PI-2@

chitosan aerogel showed almost no weight loss up to 150 °C,

indicating its less thermal stability than those of COF-PI-2

AUTHOR INFORMATION

■

Corresponding Authors

Bing-Jian Yao − College of Chemistry, Chemical Engineering

and Materials Science, Collaborative Innovation Center of

Functionalized Probes for Chemical Imaging in Universities of

Shandong, Key Laboratory of Molecular and Nano Probes,

Ministry of Education, Shandong Normal University, Jinan

250014, P. R. China; Email: yaobingjian1986@163.com

Yu-Bin Dong − College of Chemistry, Chemical Engineering

and Materials Science, Collaborative Innovation Center of

Functionalized Probes for Chemical Imaging in Universities of

Shandong, Key Laboratory of Molecular and Nano Probes,

Ministry of Education, Shandong Normal University, Jinan

(Figure 1d) and pure chitosan aerogel (Figure S47 ). However,

it completely meets the thermal stability requirement for CO₂

cycloaddition under photothermal conversion conditions.

As shown in Figure 6a, when 60 mL (630 mmol) of

epibromohydrin was used to perform the reaction within the

cup-like reactor (1.80 g aerogel, 0.5 mol % COF-PI-2 equiv,

solvent-free) under photothermal conditions (500 W xenon

−

lamp, λ > 400 nm, 80 mW cm , measured system temperature

of 45.8 °C), the CO cycloaddition reaction proceeded very

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

50014, P. R. China; orcid.org/0000-0002-9698-8863;

Article

(6) Luo, R.; Liu, X.; Chen, M.; Liu, B.; Fang, Y. Recent Advances on

^I ^m ⁱ ^d ^a ^z ^o ^l ⁱ ^u ^m ^-^F ^u ⁿ ^c ^t ⁱ ^o ⁿ ^a ^l ⁱ ^z ^e ^d ^O ^r ^g ^a ⁿ ⁱ ^c ^C ^a ^t ⁱ ^o ⁿ ⁱ ^c ^P ^o ^l ^y ^m ^e ^r ^s ^f ^o ^r ^C ^O 2

Adsorption and Simultaneous Conversion into Cyclic Carbonates.

Email: yubindong@sdnu.edu.cn

Authors

ChemSusChem 2020, 13, 3945−3966.

7) Huang, K.; Zhang, J.-Y.; Liu, F.; Dai, S. Synthesis of Porous

Luo-Gang Ding − College of Chemistry, Chemical Engineering

and Materials Science, Collaborative Innovation Center of

Functionalized Probes for Chemical Imaging in Universities

of Shandong, Key Laboratory of Molecular and Nano

Probes, Ministry of Education, Shandong Normal University,

Jinan 250014, P. R. China

Wen-Xiu Wu − College of Chemistry, Chemical Engineering

and Materials Science, Collaborative Innovation Center of

Functionalized Probes for Chemical Imaging in Universities

of Shandong, Key Laboratory of Molecular and Nano

Probes, Ministry of Education, Shandong Normal University,

Jinan 250014, P. R. China

Zhi-Gao Yu − College of Chemistry, Chemical Engineering and

Materials Science, Collaborative Innovation Center of

Functionalized Probes for Chemical Imaging in Universities

of Shandong, Key Laboratory of Molecular and Nano

Probes, Ministry of Education, Shandong Normal University,

Jinan 250014, P. R. China

Xiao-Yu Wang − College of Chemistry, Chemical Engineering

and Materials Science, Collaborative Innovation Center of

Functionalized Probes for Chemical Imaging in Universities

of Shandong, Key Laboratory of Molecular and Nano

Probes, Ministry of Education, Shandong Normal University,

Jinan 250014, P. R. China

Polymeric Catalysts for the Conversion of Carbon Dioxide. ACS

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free Hybrid Ionic Liquid (IL)-based Porous Materials for Efficient

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Functionalized Ionic Hypercrosslinked Porous Polymers for Efficient

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Y.-F.; Meng, L.-X.; Li, J. Ionic Liquid/Quaternary Ammonium Salt

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of Carbon Dioxide with Epoxides. Ind. Eng. Chem. Res. 2018, 57,

Jing-Lan Kan − College of Chemistry, Chemical Engineering

and Materials Science, Collaborative Innovation Center of

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of Shandong, Key Laboratory of Molecular and Nano

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Jinan 250014, P. R. China

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Complete contact information is available at:

https://pubs.acs.org/10.1021/acs.inorgchem.1c01975

(16) Ding, L.-G.; Yao, B.-J.; Li, F.; Shi, S.-C.; Huang, N.; Yin, H.-B.;

Guan, Q.; Dong, Y.-B. Ionic Liquid-decorated COF and Its Covalent

Composite Aerogel for Selective CO ₂ Adsorption and Catalytic

Conversion. J. Mater. Chem. A 2019, 7 , 4689 −4698.

Notes

The authors declare no competing ﬁnancial interest.

17) Liang, J.; Huang, Y.-B.; Cao, R. Metal-organic Frameworks and

Porous Organic Polymers for Sustainable Fixation of Carbon Dioxide

into Cyclic Carbonates. Coord. Chem. Rev. 2019, 378, 32−65.

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M.; Mirkhani, V.; Mohammadpoor-Baltork, I. Ionic Liquid-decorated

MIL-101(Cr) via Covalent and Coordination Bonds for Efficient

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ACKNOWLEDGMENTS

■

We are grateful for ﬁnancial support from the NSFC (grants

nos. 21971153, 21671122, and 22072077), the Major Basic

Research Projects of Shandong Provincial Natural Science

Foundation (no. ZR2020ZD32), and the Taishan Scholars

Climbing Program of Shandong Province.

Phys. Chem. C 2020, 124, 8716−8725.

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Liu, Z.-H.; Ma, J.-P.; Dong, Y.-B. Bifunctional Imidazolium-based

Ionic Liquid Decorated UiO-67 Type MOF for Selective CO

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