Development of High Yielded Sn-Doped Porous Carbons for Selective

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Development of High Yielded Sn-Doped Porous Carbons for Selective CO2 Capture Sachin Mane, Yu-Xia Li, Xiao-Qin Liu, and Lin-Bing Sun ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.9b00462 • Publication Date (Web): 16 May 2019 Downloaded from http://pubs.acs.org on May 17, 2019

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ACS Sustainable Chemistry & Engineering

Development of High Yielded Sn-Doped Porous Carbons for Selective CO2 Capture Sachin Mane, Yu-Xia Li, Xiao-Qin Liu, and Lin-Bing Sun* State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, 30 Puzhu South Road, Nanjing 211816, China. *Corresponding author. E-mail: [email protected].

ABSTRACT: The use of porous carbons for selective CO2 separation attracts increasing attention. Owing to low thermostability of porous polymers, low yield is the major concern of porous carbons. To obtain porous carbons with high yield, the development of thermostable porous polymers is highly expected. Herein, high yielded (70% for 700 oC and 64% for 800 oC)

Sn-doped porous carbons (SnPCs) have been constructed through KOH-assisted

carbonization of Sn-containing polymer. Notably, SnPC-700 (218.5 mg.g−1) demonstrates higher CO2 adsorption capacity than the reference sample prepared without KOH, SnPC-700r (188.3 mg.g−1), indicating the importance of KOH-assisted activation. Carbonization temperature has an effect on the adsorption capacity of resultant materials, and high carbonization temperature leads to better adsorption capacity on CO2. SnPC-800 is able to capture 242.8 mg.g−1 of CO2, which is better than some benchmarks including BILP-7 (193.0 mg.g−1), PAF-1-450 (196.4 mg.g−1), and FCTF-1 (205.5 mg.g−1). More importantly, SnPC800 demonstrates good selectivity of CO2 over CH4 (31.1). Thus, high yield and good performance upon CO2 adsorption capacity and selectivity over CH4 make SnPCs attractive candidates for the removal of CO2 from natural gas.

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KEYWORDS: Sn-containing polymers, Selective CO2 adsorption, Porous carbons, Carbonization, Separation

INTRODUCTION Natural gas is considered as a cost-effective energy source with increasing need.1 However, raw natural gas contains CO2 as the impurity which needs to be removed. The development of efficient technologies to eliminate CO2 from raw natural gas is thus of great significance.2 The conventional approach for CO2 removal is amine wet scrubbing, while some issues such as corrosivity of solutions and high energy consumption in regeneration should be considered.3 To overcome these difficulties, the use of adsorption over porous solids with the ability of adsorbing CO2 selectively is of great interest.4−7 Among various adsorbents, porous carbons attract much attention for CO2/CH4 separation because of well-developed porosity and high physicochemical stability. To date many attempts have been made on the preparation of porous carbons for selective CO2 adsorption. However, low yield of porous carbons is one of the major issues in fabrication of porous carbons from porous polymer precursors. This is mainly due to low thermostability of porous polymers with organic compositions. To obtain high yield, the development of thermostable porous polymers as precursors is highly expected.8,9 To extend the properties of these polymers for superior performance, some groups have developed porous carbons via the carbonization of polymers. For instance, recently the precursors TPOP-1,10

melamine

coated

poly(EGDMA-co-MAA)

spheres,11

sulfonated

poly(styrene−divinylbenzene),12 and air-carbonized sawdust13 were used to develop comparatively low yielded porous carbons including NPC-1-500 (9.8%), N-doped carbons (25.0%), porous carbons (45.9%), and activated carbon (50.0%) at the temperature of 500, 600, 800, and 800 oC, respectively. However, low yield of porous carbons is one of the major 2 ACS Paragon Plus Environment

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drawbacks. One alternative way is the synthesis of heavy metals (e.g. Sn)-containing polymers since the presence of heavy metals significantly enhances thermostability. As a result, the synthesis of heavy metals-containing polymers is interesting for the development of high-yield porous carbons, which meets the demands for purification of natural gas. In this paper, we present the facile preparation of Sn-doped porous carbons (SnPCs) with high yield and well-developed porosity. We developed NUT-16 (NUT means Nanjing Tech University) through Friedel-Craft reaction of tetraphenylstannane (TPS) and formaldehyde dimethyl acetal (FDA). The fabricated NUT-16 was employed as a precursor for the preparation of SnPCs. The carbonization yield of NUT-16 is 70% for 700 oC and 64% for 800 oC, which are the quite marked carbonization yields. The yield of porous SnPCs was remarkably increased by carbonization of Sn-containing polymer (NUT-16). Remarkably, SnPC-800 (surface area: 1790 m2.g−1) displayed high uptake of CO2 (242.8 mg.g−1) over benchmarks such as BILP-7 (193.0 mg.g−1), PAF-1-450 (196.4 mg.g−1), and FCTF-1 (205.5 mg.g−1). Furthermore, SnPC-800 exhibited high selectivity of CO2 over CH4 (31.1) as well, which make SnPCs very attractive candidates for selective CO2 capture.

EXPERIMENTAL SECTION Materials Synthesis The chemicals employed for SnPCs synthesis are as follows. Tetraphenylstannane (TPS, 97%) was procured from Aladdin. Iron (III) chloride (anhydrous) was received from Macklin. 1,2-dichloroethane (DCE, >99%) was purchased from Shanghai Lingfeng Chemical. Formaldehyde dimethyl acetal (FDA, >99.5%), potassium hydroxide, and anhydrous methanol were provided by Sinopharm Chemical, Shanghai, China. To a solution of TPS (1 g, 1 mmol) and FDA (1.32 g, 4 mmol) in anhydrous DCE (10 mL), FeCl3 (0.7 g, 4.3 mmol) dissolved in DCE (5 mL) was added under the protection of N2. 3 ACS Paragon Plus Environment


The reaction mixture was heated to 84 oC and kept at that temperature for 24 h. The obtained brown precipitate was washed with water and methanol followed by diethyl ether. Finally, synthesized polymer was dried for 24 h at 60 oC.14 The resulting brown solid was denoted as NUT-16. The monomer structure used for the fabrication of NUT-16 was depicted in Figs. 1a,b. The structure and digital photos of NUT-16 are shown in Figures 1 and S1, respectively. NUT-16 was used as a precursor for the fabrication of SnPCs.15 Typically, precarbonization of NUT-16 was conducted at 200 oC for 100 min under an air atmosphere to avoid the rapid degradation of porous structure at elevated temperature. After immersing in KOH solution, the brown solid was carbonized in N2 atmosphere at prescribed temperatures (700-800 oC) for 1 h with at a heating rate of 3 oC/min. The carbonized samples were washed with HCl (2 mmol/L) and water. The obtained samples were represented as SnPC-X, where X is the temperature for carbonization (i.e. 700 and 800 oC). A reference sample was synthesized through carbonization of NUT-16 at 700 oC in the absence of KOH, and the obtained material was denoted as SnPC-700r.

Materials Characterization Fourier-transform infrared (FTIR) spectra of NUT-16 and SnPCs were recorded on a Nicolet Nexus 470 spectrometer. . Carbon and hydrogen elemental analysis was conducted by using an Elementar Vario EL elemental analyzer. Solid-state

13C

nuclear magnetic resonance

(NMR) measurement was performed on a Bruker AVANCE 400 spectrometer Thermogravimetric (TG) data of NUT-16 were collected on a thermobalance (STA-499C, NETZSCH). Scanning electron microscopy (SEM) images of NUT-16 and SnPCs were taken on a Hitachi S4800 electron microscope. Transmission electron microscopy (TEM) images of NUT-16 and SnPCs were obtained by using a JEM-2010 UHR electron microscope. X-ray diffraction (XRD) patterns of NUT-16 and SnPCs were recorded on a Bruker D8 advance 4 ACS Paragon Plus Environment

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diffractometer with Cu Kα radiation. N2 adsorption-desorption isotherms were obtained at 77 K. The apparent surface areas were calculated by using the Brunauer–Emmett–Teller (BET) model.Pore size distributions (PSDs) were calculated from the adsorption isotherms by the Barrett-Joyner-Halenda (BJH) and non-local density functional theory (NLDFT) methods.

Adsorption Tests Adsorption isotherms of CO2 and CH4 at 273 K (ice–water bath) and 298 K (water bath) were obtained by a Micromeritics analyzer (ASAP 2020). By using the adsorption data at 273 and 298 K, the isosteric heats of adsorption (-Qst) can be calculated. The ideal adsorption solution theory (IAST) selectivity of CO2 was determined with respect to CH4 at 273 and 298 K. The IAST model based on the dual-site Langmuir-Freundlich mode was exploited as follows, S=

𝑥𝑖 𝑥 𝑗 𝑦𝑖 𝑦 𝑗

where x and y refer to the molar fractions in the adsorbed and bulk phases, and i and j represent component 1 and component 2, respectively. For the simulation, the ratio of CO2/CH4 was 50/50 (v/v).

RESULTS Structural Properties of NUT- 16 and SnPCs NUT-16 was fabricated through the Friedel-Craft reaction of TPS and FDA. NUT-16 was used as a precursor to obtain highly active SnPCs by carbonization at different temperatures. The fabricated NUT-16 and SnPCs were further subjected to different characterizations such as IR, NMR, elemental analysis, EDX, TG, DTG, XRD, SEM, TEM, and textual properties determination. IR spectra of monomer (TPS), NUT-16, and SnPCs are displayed in Figure 2A. TPS demonstrates the peak at 3065 cm−1 caused by phenyl −C−H stretching and 857 5 ACS Paragon Plus Environment


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cm−1 derived from para di-substituted −C−H stretching; the bands at 1430, 1485, and 1577 cm−1 are due to aromatic conjugated −C=C− in phenyl ring. Moreover, IR peaks of NUT-16 are also mentioned. The existence of peak at 2922 cm−1 is related to phenyl −C−H stretching, 702 cm−1 shows the presence of para di-substituted −C−H stretching, 1440, 1507 and 1602 cm−1 correspond to aromatic conjugated −C=C− in phenyl ring. Notably, the presence of 1420, 2852, 2925 cm−1 confirms the presence of methylene −C−H stretching in NUT-16; this along with the presence of IR peaks of TPS indicate the successful fabrication of NUT-16. IR spectra of SnPCs were collected as well. It is worth noting that no obvious bands were detected in the FTIR spectra of SnPCs. Thus, the presence of sharp peaks in monomer, broad peaks in NUT-16, and the absence of peaks in SnPCs demostrate the formation of carbon in SnPCs. Furthermore, NUT-16 was further characterized by solid-state

13C

NMR and

compared with the spectrum of TPS (in CDCl3). As shown in Figure 2B, 13C NMR (CDCl3, 76.9 ppm) of monomer (TPS) demonstrates the peaks at 128.6 ppm assigned to phenyl −CH− far from Sn, 129.1 ppm attributes tertiary carbon near from Sn, 137.2 ppm indicating the presence of phenyl −CH− near from Sn, and 137.9 ppm which corresponds to tertiary carbon near from Sn. NUT-16 shows the peak at 128 ppm ascribed to phenyl −CH− and 137 ppm due to phenyl tertiary carbon. The additional peak observed at 40 ppm further evidences the existence of −CH2− between two phenyl rings which confirms the formation of NUT-16. In addition to IR and NMR, NUT-16 was further subjected to organic elemental analysis. NUT16 consists of carbon (78.8 wt%) and hydrogen (4.4 wt%) only. The SnPCs were also subjected to EDX analysis which clearly indicates the presence of 11.5, 4.3, 2.0, and 1.6 wt% of Sn in NUT-16, SnPC-700r, SnPC-700, and SnPC-800, respectively (Table 1). Thus, IR and solid-state 13C NMR spectra confirm the construction of NUT-16 and SnPCs via FriedelCraft reaction and temperature-controlled carbonization, respectively. The thermostability of the fabricated NUT-16 was examined in air and nitrogen 6 ACS Paragon Plus Environment

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(Figure S2). In air, NUT-16 gave an initial and end degradation temperature at 370 and 560 oC,

respectively (Figure S2-a). The corresponding DTG plot of NUT-16 shows a peak at

about 480 oC (Figure S2-b). Similarly, thermal stability of NUT-16 was also examined in nitrogen for the same temperature range. NUT-16 revealed the initial and end degradation temperature at 300 and 900 oC, respectively (Figure S2-a). The corresponding DTG plot revealed the peak at about 500 oC (Figure S2-b). Porous carbons are widely used adsorbent family for selective gas separation. However, low yield is the major issue of porous carbons. To enhance carbonization yield, carbonization of Sn-containing polymer is one of the best ways. Herein, SnPCs with high yield were fabricated by the carbonization of Sn-containing polymer (NUT-16). Herein, NUT-16 has notable thermal stability in nitrogen atmosphere. Due to excellent textual properties and notable thermostability, NUT-16 was subjected to KOH-assisted carbonization to investigate the effect of heavy metal content in polymer, KOH-activation and activation temperature in gas adsorption. It has been reported that the presence of heavy metals such as Sn significantly enhances the thermal stability of polymers than their analogues without heavy metals, leading to high carbonization yield of porous carbons.8 In addition, the effect of KOH-activation and activation temperature is discussed.16 Thermal study demonstrates that NUT-16 has high yield in nitrogen than in air atmosphere. In nitrogen, NUT-16 predominantly decomposes at approximately 450 oC. The yield of porous carbons derived from NUT-16 is 70% at 700 oC and 64% at 800 oC in nitrogen atmosphere, indicative of a high carbonization yield from the Sn-containing precursor. Such a yield is notably higher than that of porous carbons from reported precursors including polypyrrole (4.6%, 600 oC),17 palm solid waste (34.5%, 800oC),18 porous imine-linked polymer (31.0%, 600

oC),19

poly(resorcinol–formaldehyde) (50.0%, 500

oC),20

and

microporous imine-liked polymer (50.1% at 500 oC).21 This demonstrates the high thermal stability and excellent yields of SnPCs obtained from NUT-16. In NUT-16, Sn is covalently 7 ACS Paragon Plus Environment


bonded to carbon whereas in porous carbons the covalent bonds between Sn and carbon get degraded in high-temperature carbonization process which results into the formation of Sn metal and powdered carbon. Moreover, amorphous nature of NUT-16 was confirmed by XRD measurement. Figure S3 demonstrates a broad peak at around 25° 2θ indicating the amorphous nature of organic compositions in NUT-16. SEM images of NUT-16, SnPC-700r, SnPC-700, and SnPC-800 were presented in Figure 3. SEM images show the surface morphology and some large pores in fabricated adsorbents. Similarly, TEM images of NUT-16, SnPC-700r, SnPC700, and SnPC-800 were represented in Figure 4. TEM images give some precise information of pore structure in NUT-16 and SnPCs. The textual properties are considerably important in gas separation and storage application.22,23 BET surface areas of NUT-16 and SnPCs were calculated by N2 sorption data (Figure 5a). NUT-16, SnPC-700r, SnPC-700, and SnPC-800 revealed the surface areas of 271, 944, 1375, and 1790 m2.g–1, pore volumes of 0.4, 1.4, 2.0, and 2.8 cm3.g–1, and centered pore sizes of 2.06, 1.90, 1.81, and 1.73 nm, respectively (Table 1). PSDs demonstrate that the fabricated NUT-16 and SnPCs exhibit porosities with centered pore diameter of 1.5−2.0 nm (Figure 5b). The detailed PSD of SnPC-700 is shown in Figure S4, which demonstrates the presence of few macropores. Furthermore, the PSDs of NUT-16 and SnPCs were determined by NLDFT at 77 K, indicating the coexistence of micro- and mesopores (Figure S5). The variation in textual properties is mainly due to the KOH-activation, and varied carbonization temperature. These results show the presence of high surface areas and pore volumes in SnPCs.

Gas Uptake Performance The gas (CO2 and CH4) uptake performance of NUT-16 and SnPCs was studied at two 8 ACS Paragon Plus Environment

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different temperatures. NUT-16 shows CO2 adsorption amount of 114.7 at 273 K and 79.0 mg.g−1 at 298 K (Figure 6a). NUT-16 was used as a precursor to fabricate highly active SnPCs for investigating the effect of KOH and activation temperature in CO2 adsorption. Herein, the KOH-activated SnPCs demonstrate high CO2 uptake than that prepared in the absence of KOH.24−26 This is proved by the CO2 adsorption performance of SnPC-700 (218.5 mg.g−1) and SnPC-700r (188.3 mg.g−1) (Figures 6-b,c). The collapse of larger pores takes place at elevated temperatures.27 The effect of activation temperature demonstrates that SnPC obtained from high carbonization temperature shows increased CO2 uptake than SnPC obtained from low carbonization temperature. It can be observed from the CO2 adsorption of SnPC-800, SnPC-700, and SnPC-700r which is 242.8, 218.5, and 188.3 mg.g−1, respectively (Table 1 and Figures 6-b,c,d). Notably, NUT-16 and SnPCs demonstrate much higher CO2 adsorption amount over CH4, which is related to the porous structure as well as adsorbateadsorbent interaction.28 For SnPC-800, the adsorption capacity on CH4 is 3.1 mg.g−1 while other SnPCs and NUT-16 show even lower CH4 uptake (273 K and 1 bar, Table 1). It is noticeable that, SnPC-800 (242.8 mg.g−1) demonstrates higher CO2 uptake than recently reported porous adsorbents such as network-3 (106.5 mg.g−1),29 DBF (114.0 mg.g−1),30 MAPOP-4 (135.0 mg.g−1),31 BILP-7 (122.0 mg.g−1),36 and CPOP-13 (168.0 mg.g−1)33 (273 K and 1 bar, Table 2). Similarly, the CO2 uptake of SnPC-800 (189.8 mg.g−1) is larger than some recently reported adsorbents such as NOP-3 (62.0 mg.g−1),34 HCP-4 (70.4 mg.g−1),35 BILP-16-AC (102.2 mg.g−1),32 and SNU-151ˈ (141.0 mg.g−1)37 (298 K and 1 bar, Table 2). In addition, SnPC-800 (242.8 mg.g−1) displayed remarkable CO2 capture over benchmarks such as BILP-7 (193.0 mg.g−1),36 PAF-1-450 (196.4 mg.g−1),38 and FCTF-1 (205.5 mg.g−1)39 under the comparable conditions (Table 2). The sorption isotherms of SnPC-800 at two different temperatures are depicted in Figure S6. Thus, these results clearly show the significant role of KOH-activation and activation temperature played in enhanced CO2 capture. 9 ACS Paragon Plus Environment


The CO2/CH4 selectivity was determined by IAST model. Dual-Langmuir model was used for IAST selectivity determination. The values of CO2/CH4 IAST selectivity isotherm parameters are mentioned in Table S1. Figures 7-a,b depict that SnPC-800 has selectivity of 31.1and 11.2 at 273 and 298 K, respectively. At 273 K and 1 bar, SnPC-800 demonstrates superior CO2/CH4 selectivity (31.1) over recently reported CO2/CH4 selectivity of BILP-16AC (9.0),32 PECONF-3 (10.0),40 MAPOP-4 (11.3),41 and DBF (11.6)30 (Table 2). Similarly, at 273 K and 1 bar, SnPC-800 demonstrates higher CO2/CH4 selectivity (11.2) than recently reported CO2/CH4 selectivity of PPs-BN-1-800 (5.1),41 BILP-16-AC (7.0),32 SNU-151ˈ (7.2),37 TBILP-1 (9.0),42 and DBF (10.2)30 at 298 K and 1 bar (Table 2). Thus, adsorbent with remarkable CO2 adsorption amount and excellent CO2/CH4 selectivity demonstrates their promising candidature for selective carbon capture. Isosteric heat of adsorption (-Qst) was determined from adsorption data at two different temperatures using nonlinear curve fitting (Figure S7).59 Figure 8 demonstrates that the -Qst of NUT-16 and SnPCs vary from 23 to 42 kJ.mol−1 for initial adsorption of CO2. NUT-16 and SnPCs revealed the declined -Qstwhich is caused by the occupation of active sites. The moderate heat of adsorption suggests that physisorption is predominant in the present system. Dynamic breakthrough experiments were further conducted to assess the separation performance of adsorbents. A binary CO2/CH4 (50/50) mixture was employed and the results are shown in Figure S8. In the typical adsorbent SnPC-800, CH4 breaks through the column at the initial stage within 1 min, while the breakthrough of CO2 is obviously later at around 8 min. This indicates that CH4 is weakly adsorbed on the adsorbent and the adsorption capacity on CO2 is obviously higher. A roll-up of CH4 is found on the breakthrough curve; this is because CO2 replaces CH4 when CO2 becomes predominant in the system. These results are in good agreement with static adsorption data shown above, revealing that the present 10 ACS Paragon Plus Environment

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adsorbents are promising for practical applications in purification of natural gas.

DISCUSSION NUT-16 was fabricated through Friedel-Craft reaction of inexpensive monomers and catalyst under mild reaction conditions. This can be accounted from the use of low-cost monomers (TPS and FDA), catalyst (FeCl3), and mild polymerization temperature (84 oC). It was reported that, Sn-containing polymer demonstrates high thermostability over their analogous polymer without Sn.8 High thermostability of polymer to be used for the preparation of porous carbons undoubtedly enhances carbonization yield. As a result, Sn-containing polymer was used as a precursor to obtain high yielded SnPCs. The high thermostability of NUT-16 was observed in nitrogen atmosphere (Figure S2-a) which is obviously useful for high carbonization yield (64% for 800 oC). To examine the role of KOH-activation and varied carbonization temperature, NUT-16 was employed as a precursor for the preparation of SnPCs. In carbonization, KOH-activation collapse the network resulting into the formation of porous carbons.60−62 These properties often useful in enhanced gas adsorption which can be confirmed from the CO2 adsorption by SnPC-700 (218.5 mg.g−1) and SnPC-700r (188.3 mg.g−1). Similarly, effect of carbonization temperature also significantly affects in CO2 capture enhancement. With increase in temperature, the degradation of larger pores occurs, leading to the formation of smaller pores with increased textual properties. Consequently, SnPC-800 (242.8 mg.g−1) demonstrates high CO2 uptake than SnPC-700 (218.5 mg.g−1) in similar experimental conditions. More importantly, SnPC-800 demonstrated the superior CO2/CH4 selectivity (31.1) over recently published adsorbents (Table 2).30,32 In selective CO2 capture, adsorption capacity and selectivity are two important factors. Considering both adsorption capacity and selectivity on CO2/CH4, our adsorbents are comparable to (if not better than) some reported adsorbents. Moreover, we report a strategy to greatly increase the 11 ACS Paragon Plus Environment


yield of porous carbons by Sn incorporation, which is of great importance for practical applications of these materials. Overall, it was concluded that KOH-activation and high carbonization temperature obviously demonstrates excellent CO2 uptake and superior selectivity performance over recently reported porous adsorbents. In addition, NUT-16 and SnPCs demonstrate moderate -Qst (23−42 kJ.mol−1) which indicates the enough binding capacity with ease of regeneration property of adsorbents. Thus, high yield, notable CO2 uptake, excellent selectivity, and moderate heat of adsorption make SnPCs promising in selectively capture CO2 from biogas. The present strategy may provide a clue for the design and fabrication of new porous carbon materials for various applications such as adsorption, catalysis, and sensing.

CONCLUSIONS A new type of porous carbons, SnPCs, were fabricated by KOH-assisted temperaturecontrolled carbonization of NUT-16. High yield of SnPCs was obtained by the carbonization of Sn-containing polymer (NUT-16). It is worth noting that KOH-assisted SnPC-700 (218.5 mg.g−1) demonstrates enhanced CO2 uptake than activated SnPC-700r (188.3 mg.g−1) in the absence of KOH in a similar experimental conditions. The CO2 uptake is higher (SnPC-800, 242.8 mg.g−1) for increased carbonization temperature whereas CO2 uptake decreases (SnPC700, 218.5 mg.g−1) for lower carbonization temperature under the similar conditions. Notably, SnPC-800 (242.8 mg.g−1) exhibits much higher CO2 adsorption amount than reported benchmarks including BILP-7 (193.0 mg.g−1), PAF-1-450 (196.4 mg.g−1), and FCTF-1 (205.5 mg.g−1). More importantly, SnPCsdemonstrate excellent CO2/CH4selectivity (31.1) which is remarkably higher than the recently reported benchmarks such as DBF (11.6), BILP-16-AC (9.0), PECONF-3 (10.0), MAPOP-4 (11.3), and DBF (11.6) under the analogous conditions. Owing to high carbonization yield and notable CO2 adsorption amount 12 ACS Paragon Plus Environment

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and selectivity over CH4, the newly fabricated SnPCs acts as promising candidates for selective CO2 capture from various gas mixtures such as biogas.

ASSOCIATED CONTENT The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.xxxxxx. Digital photos, TG, DTG, XRD, and nonlinear curve fitting of the resultant NUT polymers (PDF).

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected].

ORCID Lin-Bing Sun: 0000-0002-6395-312X

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This work is supported by the Science and Engineering Research Board (SERB) New Delhi, India for providing the Postdoc Fellowship, Award No.: SB/OS/PDF-341/2015-16. In addition, we acknowledge financial support of this work by the National Natural Science Foundation of China (21722606, 21676138, and 21576137). REFERENCES



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Figure 1. The chemical structures of monomers (a,b) and NUT-16.



Figure 2. (A) IR spectra of (a) TPS, (b) NUT-16, (c) SnPC-700r, (d) SnPC-700, (e) SnPC800 and (B) 13C NMR spectra of (a) TPS and (b) NUT-16.


Page 24 of 34

Page 25 of 34 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 3. SEM images of (a) NUT-16, (b) SnPC-700r, (c) SnPC-700, and (d) SnPC-800.



Figure 4. TEM images of (a) NUT-16, (b) SnPC-700r, (c) SnPC-700, and (d) SnPC-800.


Page 26 of 34

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Table 1. Textual parameters, gas uptake, and CO2/CH4selectivity performance of NUT-16 and SnPCs. Textual Propertiesa

Gas Uptakeb

Sn Selectivityc

Adsorbents

contentd

SBET (m2.g–1)

Vp (cm3.g–1)

Dp (nm)

CO2

CH4

NUT-16

271

0.4

2.06

114.7

1.9

16.2

11.5

SnPC-700r

944

1.4

1.90

188.3

2.6

27.1

4.3

SnPC-700

1375

2.0

1.81

218.5

2.9

19.6

2.0

SnPC-800

1790

2.8

1.73

242.8

3.1

31.1

1.6

aTextual

properties measured by N2 adsorption-desorption at 77 K, bGas uptake (mg.g−1)

measured at 273 K and 1 bar, cGas selectivity measured at 273 K and 1 bar, and dSn content in wt%.



Figure 5. (a) N2 adsorption-desorption isotherms and (b) pore size distributions of NUT-16 and SnPCs at 77 K.


Page 28 of 34

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Figure 6. Adsorption isotherm of CO2 and CH4 on (a) NUT-16, (b) SnPC-700r, (c) SnPC700, and (d) SnPC-800.



Page 30 of 34

Table 2. Comparison of surface area, CO2 uptake, and selective CO2/CH4 performance of different adsorbents. Adsorbents

SBETa(m2.g−1)

Tb (K)

CO2uptakec (mg.g−1)

SCO2/CH4

Ref.

SnPC-700

1375

273/298

218.5/176.0

19.6/11.9

this work

SnPC-800

1790

273/298

242.8/189.8

31.1/11.2

this work

Network-3

1159

273/298

106.5/62.5

NA

29

DBF

661

273/298

114.0/96.7

11.6/10.2

30

MAPOP-4

820

273

135.0

11.3

31

BILP-16-AC

NA

273/298

152.3/102.2

9.0/7.0

32

CPOP-13

890

273

168.0

NA

33

NOP-3

273

273/298

110.3/62.0

NA

34

HCP-4

NA

298

70.4

NA

35

BILP-7

1122

273/298

193.0/122.0

NA

36

SNU-151ˈ

1563

298

141.0

7.2

37

PAF-1-450

1191

273

196.4

9.0

38

FCTF-1

662

273/298

205.5/141.2

NA

39

PECONF-3

851

273

145.2

10.0

40

PPs-BN-1-800

215

298

101.6

5.1

41

TBILP-1

330

298

78.0

9.0

42

CuPor-BPDC

442

273/298

52.0/31.2

6.0/5.0

43

UiO-66-NH2

1080

273

171.6

7.0

44

PCTF-3

641

273

101.2

6.0

45

PCTF-1

2235

273

143.4

5.0

46

MOF-890

295

298

114.4

9.0

47


Page 31 of 34 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


ZIF-100

780

298

44.0

6.0

48

BUT-10

3040

298

171.6

5.0

49

PAF-26-COOH

717

298

66.0

4.0

50

fl-CTF600

2113

273/298

153.1/79.2

NA

51

TPI-1

809

298

55.0

9.0

52

CMP-1-COOH

522

273

66.0

NA

53

AlPO4-17mPCP650

464

298

61.6

NA

54

CTF-DCN-500

735

298

75.4

9.7

55

NAPC-2-6

1247

273/298

251.0/172.0

12.1/10.1

56

SNMC-2-600

1884

273/298

324.7/186.6

6.3/4.3

57

NUT-11

598

273/298

198.0/96.8

107/26

58

aBET

surface areas were measured by N2 adsorption-desorption isotherm at 77 K. bCO2

uptake and selectivity measured temperature. cCO2 uptake at 1 bar. NA: not available.



Figure 7. IAST selectivity of CO2/CH4 on NUT-16 and SnPCs at (a) 273 and (b) 298 K.


Page 32 of 34

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Figure 8. CO2 isosteric heat of adsorption of NUT-16 and SnPCs.



For Table of Contents Use Only Synopsis: Porous carbons derived from a Sn-doped polymer show enhanced yield, high CO2 uptake and excellent CO2/CH4 selectivity.


Page 34 of 34

Development of High Yielded Sn-Doped Porous Carbons for Selective

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