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Knitting Aryl Network Polymers Incorporated Ag Nanoparticles: A Mild and Efficient Catalyst for the Fixation of CO2 as Carboxylic Acid Zhilian Wu, Qinggang Liu, Xiaofeng Yang, Xue Ye, Hongmin Duan, Jian Zhang, Bo Zhao, and Yanqiang Huang ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b02678 • Publication Date (Web): 10 Oct 2017 Downloaded from http://pubs.acs.org on October 13, 2017

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ACS Sustainable Chemistry & Engineering

Knitting Aryl Network Polymers Incorporated Ag Nanoparticles: A Mild and Efficient Catalyst for the Fixation of CO2 as Carboxylic Acid Zhilian Wu,†,‡,§ Qinggang Liu,‡, Xiaofeng Yang,* ,‡ Xue Ye,‡ Hongmin Duan,‡ Jian Zhang,‡ Bo Zhao,φ and Yanqiang Huang*,‡ †

CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy

Conversion, Chinese Academy of Sciences, No.2 Nengyuan Road, Wushan street, Guangzhou 510640, China. ‡

State Key Laboratory of Catalysis, iChEM (Collaborative Innovation Center of

Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, No.457 Zhongshan Road, Dalian 116023, China. φ

State Key Laboratory of Advanced Power Transmission Technology (Global Energy

Interconnection Research Institute), Changping District, Beijing 102211, China. §

University of Chinese Academy of Sciences, No.19 (A) Yuquan Road, Shijingshan

District, Beijing 100049, China.

*Corresponding

author

E-mail

address:

[email protected];

[email protected]

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KEYWORDS: Carbon dioxide, Porous organic polymers, Heterogeneous catalyst, Alkynyl carboxylic acid

ABSTRACT: A simple and scalable method for synthesizing silver nanoparticles supported on the framework of mesoporous knitting aryl network polymers (KAPs) has been developed. With the benefits from its mesoporous texture and the stabilizing effect of phosphine compounds in the matrix, the silver precursor can be efficiently introduced into the KAPs framework, which results in a nano-size distribution of Ag (ca. 4.1 nm) supported on KAPs (Ag/KAPs-P) with narrow particle size distribution and homogeneous dispersion after simple reduction step. The as-obtained small metal sized Ag/KAPs-P catalyst is particularly active for the direct carboxylation of terminal alkynes with CO2 into carboxylic acid at low temperature and atmospheric pressure. Moreover, this Ag/KAPs-P catalyst also shows high stability under the reaction conditions, it can be recycled at least five times without significant loss of activity, suggesting its great potential application in the heterogeneous conversion of CO2 into carboxylic acid.

INTRODUCTION

The excessive emission of CO2 due to the increased usage of fossil fuels has become an urgent issue as it causes a series of environment problems.1-4 While on the other hand, in terms of its non-toxicity, renewability, and accessibility, CO2 is also considered as a “green” carbon source,5-7 thus the conversion of CO2 into chemicals has attracted ever-increasing interests.8-11 Among them, the formation of C-C bonding 2 ACS Paragon Plus Environment

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products is one of the most promising avenues,12,13 in which the carboxylic acid is the most facile product owing to its similarity in form to the parent CO2. More importantly, the carboxylic acid can serve as not only key structural motifs in medical chemistry, but also versatile building blocks for the construction of bioactive molecules and conductive polymers.14-17 Recently, several homogeneous catalytic processes have been reported, however, the further application was severely hampered by either the recycling problems or the high ligand sensitivity to water or air.18-20 Thereafter, a few heterogeneous metal catalysts for this reaction have also been reported, but the performance of supported catalysts is still underdeveloped due to their poor yield of desired product, harsh reaction conditions, or difficult catalyst preparation.21-25 More recently, we have successfully prepared a Schiff-base modified silver catalyst on the silica support, which shows an excellent activity.26 Even so, the sizes of silver nanoparticles are not well dispersed due to the easy aggregation of silver nanoparticle in the preparation process, which limits its catalytic performance in the carboxylation of alkynes. Therefore, the development of a more efficient and robust heterogeneous Ag nano-catalyst featuring simple, green and scalable preparation is still in great demand, yet remain challenging.

Porous organic polymers (POPs) have recently created new opportunities for the development of heterogeneous catalysis.27,28 Particularly, Tan and his colleagues have reported a low-cost strategy to synthesize high surface area knitting aryl network polymers (KAPs) by using a simple one-step Friedel-Craftsreaction.29-31 KAPs have several interesting advantages, such as a simple synthesis method, and different kinds 3 ACS Paragon Plus Environment


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of monomers that give diverse functional polymers.29,32 Accordingly, it can be imagined that with KAPs as a support for silver nanoparticles, it can be more beneficial to distribute metal nanoparticles on the support by the mesopores and/or functional-group modification,33 which then would offer great opportunity for performance promotion in this direct carboxylation reaction. Herein, we report a simple route to prepare a series of novel Ag/KAPs catalysts by NaBH4 reduction of silver precursors under room temperature. Moreover, by modification of KAPs with phosphine, the Ag/KAPs-P catalyst can be homogeneously dispersed on the support with small size distribution and act as an excellent catalyst with good recyclability in the conversion of CO2 to alkynyl carboxylic acids under mild reaction conditions.

RESULTS AND DISCUSSION KAPs with or without the modification of Triphenylphosphine (PPh3) in the matrix (Scheme S1) were used as supports to anchor Ag NPs to form Ag/KAPs-P and Ag/KAPs-Py catalysts by the reduction of silver tricyanomethanide (AgTCM) precursor, or by using AgNO3 as a precursor to prepare the Ag*/KAPs-Py sample, as seen in Scheme 1, and Supporting Information (SI) for experimental details. All these three catalysts have the same Ag loadings of 0.1 wt%, which were detected by inductively coupled plasma atomic emission spectroscopy (ICP-AES).

The successful growth of network with PPh3 and pyrrole functional groups were confirmed by Fourier transform infrared (FTIR) spectroscopy, high resolution scanning electron microscope-energy dispersive spectroscopy (HRSEM-EDS), 4 ACS Paragon Plus Environment

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elementary analysis (EA) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). FTIR spectroscopy of KAPs-P and KAPs-Py (Figure S1)

Scheme 1. Synthetic route of: a) Ag/KAPs-P, b) Ag/KAPs-Py and c) Ag*/KAPs-Py. Magenta balls represent PPh3 functional groups, green balls represent Ag NPs. Solid line represents boundary of material particles. Dashed lines represent inner network of material particles.



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display a series of bands around 1630–1615, 1250–950, and 900–650 cm−1 which can be attributed to benzene or pyrrole skeleton stretching, C–H out-of-plane bending and in-plane bending vibrations of the benzene ring, while the peaks at 1439 cm−1 and 1448 cm−1 belonged to the vibrations of the P–CH2 bond and C-N-C skeleton, respectively.31 The morphology of the KAPs was investigated by HRSEM-EDS (Figure 1). It was revealed of the formation of solid spheres with sub-micrometer dimensions for KAPs-P and aggregated nanoparticles for KAPs-Py. The element maps (EDS) for KAPs-P (Figure S2) confirmed that N and P were homogeneously distributed throughout the KAPs-P matrix. Further analysis of the networks by element analysis (EA) and ICP-AES indicates KAPs-P was mainly composed of C (58.29 wt%), H (3.68 wt%), N (4.77 wt%) and P (1.58 wt%), while KAPs-Py contained C (54.86 wt%), H (3.79wt%) and N (11.04 wt%).

Figure 1. SEM images of (a) KAPs-P and (b) KAPs-Py.

The CO2 sorption properties of samples KAPs-P and KAPs-Py were then investigated at room temperature and atmosphere pressure (Figure2). The uptakes of CO2 were 17.2 and 24.3 cm3/g for KAPs-P and KAPs-Py, respectively. These values are comparable with those well-known POPs materials under identical conditions,34, 35 indicative of the good sorption capacity of KAPs toward CO2, which might be 6 ACS Paragon Plus Environment

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beneficial for the following conversion of CO2. The porous properties of KAPs-P, KAPs and corresponding catalysts were measured by N2 sorption analysis. Significant decreases in the amount of N2 sorption and the size of pore diameter were observed for both Ag-loaded samples in comparison with the corresponding supports. The decrease in the SBET and pore volume should be attributed to the incorporation of the Ag NPs into the pores of KAPs and/or a block of Ag NPs located on the framework surface of KAPs (Figure S3, Table S1).

30 KAPs-Py KAPs-P

25

CO2 uptake (cm3/g)

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20 15 10 5 0 0.0

0.2

0.4

0.6

0.8

1.0

P (atm)

Figure 2. CO2 adsorption/desorption (298 K) of KAPs-P and KAPs-Py. Ag NPs immobilized in KAPs-P and KAPs-Py was characterized by Powder X-ray diffraction (PXRD) patterns, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The PXRD patterns in Figure S4 show that no silver peaks were observed for all the as prepared Ag catalysts (Ag/KAPs-P, Ag/KAPs-Py and Ag*/KAPs-Py) due to the low loading of silver on the support. X-ray photoelectron spectroscopy (XPS) result (Figure 3) of Ag/KAPs-P indicated that the silver ions were successfully reduced to Ag (0) nanoparticles by the NaBH4. To further study the Ag/KAPs catalysts, the morphology of the silver NPs deposited 7 ACS Paragon Plus Environment


on the support of KAPs was characterized by high resolution transmission electron microscopy (HRTEM). The HRTEM images (Figure 4) confirmed that the silver NPs in Ag/KAPs-P were homogeneously dispersed with a smaller size (4.1±1.4 nm) than that in Ag/KAPs-Py (9.8±5.4 nm) and Ag*/KAPs-Py (17.5±9.6 nm). This can be explained by the promotion effect of phosphine in the dispersion and stabilization of Ag components.33, 36-49 For one thing, the p-electron pair of P leads it as an efficient ligand for the Ag precursor, which can promote ligand exchanges with the AgTCM, and help to disperse Ag precursors into the mesoporous of KAPs. For another, it is also beneficial to the anchoring of Ag nanoparticles, which hampers its aggregation during the reduction process. As a result, a small sized Ag nanoparticle can be facilely obtained over KAPs-P materials.

Agfresh 3d5/2 = 368.3 eV Agrecycled 3d5/2 = 367.8

Ag 3d5/2

Ag 3d3/2

Intensity (a. u.)

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fresh

recycled

380

378

376

374

372

370

368

366

364

362

Binding energy (eV)

Figure 3. XPS spectra (Ag-3d levels) of the fresh and the recycling used Ag/KAPs-P catalyst.


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Figure 4. HR-TEM images of (a) Ag/KAPs-P, (b) Ag/KAPs-Py, (c) Ag*/KAPs-Py, and (d) the recycled Ag/KAPs-P catalysts. The insets are the corresponding metal size distributions.

The comparative catalytic activities of the Ag/KAPs catalysts were evaluated for the conversion of CO2 with terminal alkynes into propiolic acids. In our initial investigation, the carboxylation of 1-ethynylbenzene was selected as a model reaction to investigate the influence of various parameters on the reaction. It has found that, under the conditions of 60 oC, 1.0 atm of CO2 and 6 h, the reaction in DMSO gave only 37% yield in the absence of catalyst, and the only presence of KAPs-P shows no contributions on the yield of product (entries 1-2 in Table 1). In contrast, when the Ag/KAPs-P catalyst was added as a catalyst, the yield was greatly promoted to 74%



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Table 1. Synthesis of 3-phenylpropiolic acid from CO2 and 1-ethynylbenzene.[a] Entry

Catalyst

Base

Solvent

T

Yield

1

None

Cs2CO3

DMSO

60

37%

2b

KAPs

Cs2CO3

DMSO

60

37%

3

Ag/KAPs-P

Cs2CO3

DMSO

60

74%

4

Ag/KAPs-Py

Cs2CO3

DMSO

60

66%

5

Ag*/KAPs-Py

Cs2CO3

DMSO

60

59%

6

Ag/KAPs-P

Na2CO3

DMSO

60

Trace

7

Ag/KAPs-P

K2CO3

DMSO

60

2%

8

Ag/KAPs-P

KTB

DMSO

60

20%

9

Ag/KAPs-P

Cs2CO3

Dioxane

60

trace

10

Ag/KAPs-P

Cs2CO3

MeCN

60

2%

11

Ag/KAPs-P

Cs2CO3

PC

60

3%

12

Ag/KAPs-P

Cs2CO3

DMF

60

5%

13

Ag/KAPs-P

Cs2CO3

DMSO

40

29%

14

Ag/KAPs-P

Cs2CO3

DMSO

50

55%

15

Ag/KAPs-P

Cs2CO3

DMSO

70

83%

16

Ag/KAPs-P

Cs2CO3

DMSO

80

89%

17b

Ag/KAPs-P

Cs2CO3

DMSO

60

92%

[a] Reaction conditions: 1-ethynylbenzene (1.0 mmol), catalyst (10 mg), base (1.5 mmol), CO2 (1.0 atm), solvent (5 mL), 6 h. [b] with KAPs-P or KAPs-Py as a catalyst. [c] Reaction time was extended to 10 h.

(entry 3, Table 1). As a reference catalyst, however, Ag/KAPs-Py gave a relatively poor yield (66%, entry 4 in Table 1), which was likely due to its larger metal sizes (9.8±5.4 nm) compared with that of Ag/KAPs-P catalyst. Correspondingly, the 10 ACS Paragon Plus Environment

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Ag*/KAPs-Py catalyst resulted in the lowest yield (59%, entry 5 in Table 1) owing to its largest metal particle size in these three samples. Cs2CO3 is one of the most commonly used bases in various organic reactions.50 Here, Cs2CO3 was also considered as the superior choice for this carboxylation reaction of 1-ethynylbenzene with CO2, which is consistent with the results in previous reports.18, 21, 26 Among those other bases we screened, Na2CO3, K2CO3 and potassium tertbutoxide (KTB) resulted in rather poor yields (entries 6-8 in Table 1). Moreover, the impact of the polar organic solvents was proved to be the other key factor influencing this reaction, and dimethyl sulphoxide (DMSO) was the best one. That is, under the conditions of 60 °C and 1.0 atm of CO2, 74% yield was obtained in DMSO over Ag/KAPs-P catalyst (entry 3 in Table 1), while only trace, 2%, 3%, and 5% yields were obtained in the solvents of 1,4-dioxane (Dioxane), acetonitrile (MeCN), propylene carbonate (PC) and N, N-dimethylformamide (DMF), respectively (entries 9-12 in Table 1). Therefore, both the base and solvent are important factors in determining the high yield of CO2 to carboxylic acid, and the combination of Cs2CO3 with DMSO plays an important role on the high yield toward carboxylic acid. It was deduced that the stronger polar solvent (DMSO) may promote the dissolution of Cs2CO3 in liquid phase, which was responsible for alkynes to free the terminal protons by forming the Ag-C intermediates for further carboxylation. Similar solvent effect of DMSO in the carboxylation of terminal alkynes was also found in our or other reported studies.19,26 Accordingly, according to our previous results, the same mechanism for the carboxylation of terminal alkynes was proposed over this 11 ACS Paragon Plus Environment


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Ag/KAPs-P catalyst, that is, the terminal alkyne was first coordinated to the small sized silver NPs on KAPs-P, and was then deprotonated by the Cs2CO3 in liquid phase to generate a silver acetylide intermediate, which was finally inserted with the carbon dioxide into its C-Ag bond to form the carboxylate. The synergistic effect between silver NPs and Cs2CO3 can thus extremely enhanced the catalytic activity of this nanocatalyst system,21, 25, 26 and the small sized Ag nanoparticles might promote the generation of silver acetylide intermediate on the catalyst.

The influence of temperature on this carboxylation reaction was also studied, and it was proved that the catalytic performance of Ag/KAPs-P increased with the increase of the temperature (entries 3, 13-16 in Table 1). Giving overall consideration to the temperature and activity, 60 °C was selected as an optimal temperature. Meanwhile, when reaction time was extended to 10 h, a higher yield (92%) can be obtained (entry 17 in Table 1), and the Ag/KAPs-P catalyst has a large turn-over number (TON, based on Ag content) of 9936, to the best of our knowledge, which is the best one ever reported for the catalytic conversion of CO2 into alkynyl carboxylic acid (Table S2).

In order to investigate the general application of such Ag/KAPs-P catalyst in the carboxylation reaction, the scope with respect to various other terminal alkyne substrates was then explored (Table 2). Under the optimal conditions, with Ag/KAPs-P (0.01mol% of Ag), 1.5 equivalents of Cs2CO3, 5mL DMSO, 60 °C and 1.0 atm CO2, the corresponding carboxylation products were achieved in promising yields (85-98 %) regardless of aromatic alkynes with either the stronger 12 ACS Paragon Plus Environment

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electron-donating substituent (Table 2, entry 2) or with electron-withdrawing groups (Table 2, entries 3-4). A heterocyclic 3-ethynylthiophene was also tested and a yield of 87% was achieved (entry 5 in Table 2). Both the alkyl- and alkenyl-substituted Table 2 Substrate scope tests over the 1c catalyst[a]

Entry

Alkyne

Product

Yield[b]/%

1

92

2

89

3

93

4

98

5

87

6

89

7

85

[a] Reaction conditions: alkyne (1.0 mmol), Ag/KAPs-P (10 mg), Cs2CO3 (1.5 mmol), CO2 (1.0 atm), 60°C, DMSO (5 mL), 10 h. [b] Isolated yields.

terminal alkynes are also suitable to this procedure, thus giving the target alkynyl carboxylic acids in synthetically satisfactory yields of 89% and 85%, respectively 13 ACS Paragon Plus Environment


(entries 6-7 in Table 2). As a result, Ag/KAPs-P catalyst can be widely and efficiently used in the CO2 fixation by terminal alkynes as carboxylic acids.

100

80

Yield / %

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60

40

20

0 1

2

3

4

5

Recycling number

Figure 5. Recycling tests of Ag/KAPs-P catalyst for the carboxylation of terminal alkynes with CO2. Reaction conditions: 1-ethynylbenzene (1.0 mmol), catalyst (10 mg), Cs2CO3 (1.5 mmol), CO2 (1.0 atm), DMSO (5 mL), 10 h, 60 °C (blue) or 40 °C (gray).

Finally, the reusability of the Ag/KAPs-P catalyst was investigated by using the carboxylation of 1-ethynylbenzene to the corresponding 3-phenylpropiolic acid as an example. For each run, the reaction was carried out under the 1 atm pressure at 40 or 60 °C reaction temperature for 10 h (Figure 5). The catalyst after each run was filtered and washed with H2O and ethanol, followed by drying to remove the residues from the surface of Ag/KAPs-P. The catalytic activity of Ag/KAPs-P can retain its high yield toward 3-phenylpropiolic acid more than five times in the two series of experiments, and only a slight decrease in activity at 60 °C was observed with the yields ranging from 84% to 92%. It can be attributed to the durability of Ag NPs in 14 ACS Paragon Plus Environment

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the KAPs-P support during the reaction, which can hinder the great aggregation of Ag NPs in the reaction. Indeed, as suggested by the HRTEM image of Ag/KAPs-P catalyst after five runs (Figure 4), the particle size of Ag NPs was only slightly aggregated, with a particle size of 6.0±2.2 nm, confirming the good stability of Ag/KAPs-P during reaction process. Meanwhile, the XPS spectra of the recycled Ag/KAPs-P catalyst (Figure 3) indicated that the peak of 3d5/2was shifted from 368.3 to 367.8 eV, which may due to the partial oxidation of Ag NPs in the solvent of DMSO during the reaction.

CONCLUSION

In conclusion, we have developed a new kind of KAP material with phosphine in its framework for supporting Ag nanoparticles. Thanks to the P anchoring sites in the matrix, silver nanoparticles can be introduced homogeneously into the mesoporous KAPs-P framework by with the AgTCM as a precursor. Due to its small size of metal active sites, the as-prepared Ag/KAPs-P catalyst exhibits efficient activity toward the direct carboxylation of terminal alkynes with CO2 to produce valuable carboxylic acids under the stronger polar solvent (DMSO), in which the dissolution of Cs2CO3 promotes to free the terminal protons of alkynes and form the Ag−C intermediate. Moreover, the stabilizing effect of phosphine also contributes to the anti-aggregation of silver nanoparticles under the reaction conditions, and the Ag/KAPs-P catalyst can be recycled five times without significant loss of activity. Such Ag/KAPs-P catalyst is of great potential application in the heterogeneous conversion of CO2 into carboxylic 15 ACS Paragon Plus Environment


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acid, and the synthesis route can also be extended to other metal NPs catalysts supported on KAPs-P.

ASSOCIATED CONTENT

Supporting Information

The Supporting Information is available free of charge on the ACS Publications web site at DOI: 10.1021/acssuschemeng.7b00xxx.

Experimental details, materials, methods, and characterizations, Table S1-S2, Figure S1–S4, and Scheme S1 (PDF)

AUTHOR INFORMATION Corresponding Author *Xiaofeng Yang. Fax: +86 411-8468-5940; E-mail: [email protected]

*Yanqiang Huang. Fax: +86 411-8468-5940; E-mail: [email protected]

ORCID

Yanqiang Huang: 0000-0002-7556-317X

Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Notes 16 ACS Paragon Plus Environment

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The authors declare no competing financial interest.

ACKNOWLEDGMENT The authors acknowledge the financial support from the National Natural Science Foundation of China (21403218, 21476226, 21503125, 21506204 & 21776269), China Ministry of Science and Technology under contact of 2016YFB0600902, National Key R&D Program of China (2016YFA0202804), State Grid Cooperation of China (SGRI-DL-71-16-015), Dalian Science Foundation for Distinguished Young Scholars (2016RJ04), the Youth Innovation Promotion Association CAS. The authors also appreciate valuable discussions with Mr Jiawei Zhong, and Dr Yancheng Hu.

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Knitting aryl network polymers (KAPs) with incorporated silver nanoparticles were successfully developed as a mild and efficient catalyst for the direct carboxylation of various terminal alkynes under one atmospheric pressure of CO2 at 60 oC.


Knitting Aryl Network Polymers-Incorporated Ag ... - ACS Publications

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