N-doped Porous Carbon Derived by Direct Carbonization of Metal

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N-doped Porous Carbon Derived by Direct Carbonization of Metal–Organic Complexes Crystal Materials for SO2 Adsorption Ani Wang, Ruiqing Fan, Xinxin Pi, Sue Hao, Xubin Zheng, and Yulin Yang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01925 • Publication Date (Web): 05 Feb 2019 Downloaded from http://pubs.acs.org on February 6, 2019

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Crystal Growth & Design

1

N-doped Porous Carbon Derived by Direct Carbonization of Metal–Organic

2

Complexes Crystal Materials for SO2 Adsorption

3

Ani Wang,a Ruiqing Fan,*,a Xinxin Pi,b Sue Hao,a Xubin Zhenga and Yulin Yang*,a

4 5 6 7 8 9 10 11 12 13

a

14

and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of

15

Technology, Harbin 150001, P. R. of China

16

b

17

150001, China.

MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion

School of Energy Science and Engineering, Harbin Institute of Technology, Harbin,

18 19

Corresponding Author: * Ruiqing Fan and Yulin Yang

20

E-mail: [email protected] and [email protected]

21 22 23 24 1

ACS Paragon Plus Environment

Crystal Growth & Design 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

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Abstract: Three Metal–Organic Complexes crystal materials (MOC-1, MOC-2 and

2

MOC-3) have been hydrothermally synthesized. Driven by C–H···O and C–H···Cl

3

hydrogen

4

supramolecular metal–organic frameworks with pcu, bnn, dia topology, respectively.

5

Subsequently, N-doped porous carbons (NPCs) were obtained from carbonization of

6

three Metal–Organic Complexes (MOCs) crystal materials. The resulting NPCs were

7

multi-walled graphite type structure, with high BET surface area (3186.5 m2 g-1), pore

8

volume (2.16 cm3 g-1) and high nitrogen content (19.6%), N atom of the MOCs

9

precursor mostly retained. Especially, benefiting from largest surface area, micropore

10

structure, more disordered stacks of carbon layers, the largest displacement distance

11

of D band and G band, NPCs showed a significant amount of SO2 adsorption

12

capacity, up to 156.72 mg g-1. The SO2 adsorption capacity increased remarkably over

13

12 times when addition of O2 and H2O together. Theoretical calculation indicated that

14

N doping into N-doped porous carbons remodels the local electronic density as well

15

as electrostatic surface potential enhancing the SO2 adsorption. This work

16

demonstrate a clear and significant advance for preparing the N-doped porous carbon

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materials from metal-organic complexes to effectively SO2 adsorption.

18

 INTRODUCTION

bonding

interactions,

MOC-1,

MOC-2

and

MOC-3

displayed

19

Sulfur dioxide (SO2) emission rise considerably in the recent decades due to the

20

combustion of fossil fuels. One of the most effective SO2 capture technology is Flue

21

gas desulfurization (FGD).1,2 Although traditional FGD technologies have been

22

commercialized in industrial processes, some inherent drawbacks still exist.3,4 For 2


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1

instance, limestone scrubbing frequently brings forth a large amount of byproduct,

2

eg., solid wastes (CaSO4), waste water. Most important of all, through such

3

technology, the sulfur resources cannot be well recycled. The content of sulfur

4

emission for raw materials such as coal and petroleum has gradually increased in

5

recent years. Therefore, limestone washing technology will inevitably generate more

6

solid waste and consume more adsorbents.5-8 Therefore, there is an urgent need to

7

develop green, effective, economical and reversible absorbents that can adsorption

8

SO2.

9

Recently, removal of SO2 by porous solids, especially, porous carbons derived

10

from Metal–Organic Complexes have attracted much attention.9-13 Porous carbons

11

derived from MOCs exhibit multifaceted advantages, 14-18 for example, high chemical

12

and thermal stability, metal-free framework, lightweight, ease of regeneration and

13

tunable textural properties.19-21 A few of MOCs have been tailor-made and carbonized

14

to produce heteroatom-doped porous carbons for environmental applications and

15

clean energy.22-26 Structures or properties of the porous carbons derived from MOCs

16

can be adjusted and controlled by introducing N, O, S, P, B or any other heteroatoms

17

to achieve various applications, for example, gas storage and separation, energy

18

storage and heterogeneous catalysis.27-31 Especially, carbonization of porous

19

framework structure like MOCs led to multifunctional porous carbons.32,33 Hence,

20

recent research is dedicated to enhance porosity and promote heteroatoms chemical

21

modification to enhance gas uptake.25,34

22

In this study, for the first time, three novel Metal–Organic Complexes crystal 3



1

materials (MOC-1, MOC-2 and MOC-3) are as precursors to prepare graphite

2

nano-sheets type porous carbon (NPC-1, NPC-2 and NPC-3) through the

3

carbonization process. The BET surface area and pore volume obtained from N2

4

isotherms are 3186.5, 2252.1 and 2426.2 m2 g-1 and 2.1562, 1.3562, 1.4631 cm3 g−1,

5

respectively. Especially, the surface area and nitrogen contentof NPC-1 reaches as

6

high as 3186.5 m2 g−1 and 19.6%, therefore, the NPC-1 shows 156.72 mg g-1 SO2

7

adsorption. Subsequently, theoretical calculation indicated that the introducation of N

8

could effectivity change the local electronic density as well as electrostatic surface

9

potential, for enhancing SO2 capature. MOC-1 as precursors to prepare the NPC-1

10

through the carbonization process is schematically shown in Scheme 1.

11

Scheme 1. Scheme of MOC-1 as precursors to prepare the NPC-1 through the carbonization.

12 13 4


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 RESULTS AND DISCUSSION

2

It has been reported in the literature that hetero atom dopant modification (e.g.,

3

Fe, P, S, Co, N, O) can very effectively affect the adsorption of acid gases by porous

4

carbon materials,25,35 for preparing carbons materials decorated by heteroatom-doped,

5

the most critical and primary step is the selection of carbon sources. Herein, three

6

novel N-doped carbon (NPCs) were synthesized using metal–organic complexes as

7

the heteroatom-doped carbon sources. In this work, all the MOCs crystalline materials

8

have never been reported in the literature. In the case of MOC-1, the mixture of

9

6-methoxy-2-pyridinecarboxaldehyde, p-aminobenzoic acid and ZnCl2 in acetonitrile

10

solution were stirring for 1h at room temperature, following by refluxing at 90 °C for

11

12 h using one-pot method (Scheme 1). Final mixture solution was filtered,

12

evaporated after the end of reaction, resulting ultimate formation of yellow crystals.

13

Crystal structure of Metal–Organic Complexes

14

Structural description of MOC-1

15

The crystal structure of MOC-1 is shown in Figure 1a, which including two Zn2+

16

ions, an uncoordinated acetonitrile molecule, two ligands and four chloride ions.36,37

17

Especially, the coordination of Zn (II) ion with pyridinium and imine nitrogen forms a

18

five-membered ring, making the entire compound exhibit a greater degree of

19

conjugation than the ligand. Each central metal Zn2+ presents contorted octahedral

20

configuration [ZnN2Cl2] (Figure S1).38-43 Individual MOC-1 molecule is construct to

21

dimer Figure S2) and 1D chain through C11–H11A···O6 and O4–H4···O2 hydrogen

22

bonding interactions, H4···O2 and H11A···O6 distances are 1.850 Å and 2.690 Å 5



1

(Figure 1b), respectively.44-46 The chain structures were linked into a 3D network

2

structure through C12–H12A···Cl3, C22–H22A···Cl3 and C12–H12A···O3 hydrogen

3

bonding interactions finally (Figure 1c). Calculation results of PLATON

4

demonstrated that a total solvent-accessible volume reached as 710.8 Å3, which

5

accounted for 10.3% percent of the entire cell volume (6878.0 Å3),38-43 as is shown in

6

Figure 1d. Moreover, individual MOC-1 molecule is regarded as point of junction,

7

and C–H···O and C–H···Cl as linkers, the 3D network structure of MOC-1 was

8

simplified a pcu topology structure for the point of {412·63} (Figure S3).47-50

9 10

Figure 1. (a) Crystal structure of MOC-1. (b) 1D chain and (c) 3D network structure of MOC-1.

11

(e) Micropore stucture of MOC-1. Some atoms omitted for clarity. Yellow and blue dotted lines

6


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1

represent the C–H···O and C–H···Cl hydrogen bonding interactions. Some H atoms are omitted

2

for clarity.

3


4

For each asymmetric unit of MOC-2, one Zn2+ ions, one imine-based ligand and

5

two chloride ions was included (Figure 2a). The independent unit of MOC-2 are

6

firstly constructed into dimer (Figure 2b), 1D chain (Figure S4), 2D layer (Figure 2c)

7

and then construct 3D network through C–H···Cl/O hydrogen bonding (Figure 2d).

8

38-42

9

MOC-2 molecule is connected with 8 adjacent MOC-2 molecules through

10

noncovalent bonding. Regarding the MOC-2 asymmetric unit as 5-connected node,

11

and the C–H···Cl and C–H···O hydrogen bonding interactions as connection lines,

12

MOC-2 exhibits 3D bnn topology with the point symbol of {46·64}.48-50 (Figure 2e)

Detailed analysis of the supramolecular structure of MOC-2 shows that each

13 14

Figure 2. (a) Structure of MOC-2. (b) Dimer of MOC-2. (c) 2D layer and (d) 3D network

15

structure in MOC-2. (e) Topological structure of the 3D network for MOC-2. Some H atoms that

16

not involved in forming hydrogen bonds omitted for clarity. 7



1


2

Single crystal X-ray diffraction analysis demonstrated that MOC-3 (Figure 3a)

3

crystallize in the triclinic crystal. Introducing the Zn(II) ion result in the metal

4

coordinated with the phenanthroline N, imine N to form a lager conjugation system

5

containing five rings in the same plane and the formation of two new five-membered

6

rings. Five-coordinated (ZnN3Cl2) trigonal bipyramidal coordination geometry was

7

formed, two N atoms from phenanthroline-N, one N atom from imine-N, and two Cl

8

atoms. The independent asymmetric units of MOC-3 are linked through C13–

9

H13A···Cl2, C16–H16A···Cl1, C3–H3A···Cl2 and C8–H8A···Cl2 hydrogen bonding

10

interactions to generate 1D chain, 2D layer (Figure 3b) and 3D network (Figure 3c).

11

Considering noncovalent bond (C–H···Cl and C–H···O interactions) as linkers and

12

the MOC-3 as 4-connected node, 3D dia topology (Figure 3d) was formed for the

13

supramolecular structure of MOC-3 with the point symbol of {66}.

14 15

Figure 3. (a) Structure of MOC-3. (b) 2D layer and (c) 3D supramolecular structure of MOC-3.

16

Some H atoms that not involved in forming hydrogen bonds omitted for clarity. (d) Topological

17

structure of MOC-3. 8


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1

Crystallographic data and structural refinement51,52 for MOCs are listed in Table

2

1. Part of the bond angles and bond lengths of MOC-1, MOC-2 and MOC-3 are listed

3

in Table S1. CCDC reference number: 1850639, 1850640 and 1850641, respectively.

4

Table 1. Structural refinement and crystallographic data for MOC-1, MOC-2 and MOC-3. CCDC No. Formula

MOC-1 1850639 C30H27O6N5Cl4Zn2

MOC-2 1850640 C17H12O2N2Cl2Zn 412.56

MOC-3 1850641 C25H17N3Cl2Zn 495.69

Mr

826.15

Crystal system

Monoclinic

Triclinic

Space group

Monoclinic C2/c

P21/c

a [Å]

47.713(9)

11.411(2)

P1 8.9852(18)

b [Å]

10.108(2)

11.712(2)

10.090(2)

c [Å]

12.596(3)

13.005(3)

α [˚] β [˚] γ [˚] Volume [Å3]

14.615(3) 90 102.64(3) 90 6878(2)

90 92.91(3) 90 1681.3(6)

76.01(3) 89.15(3) 66.40(3) 1043.9(4)

Z

8

4

2

1.596

1.630

1.577

1.755

1.790

1.451

F (000)

3343

832

504

Θ range [˚]

3.43–27.56

2.92–27.63

1.62–26.77

h range

-62 ≤ h ≤ 62

–14 ≤ h ≤ 14

–11 ≤ h ≤ 11

k range

-13 ≤ k ≤ 13

–15 ≤ k ≤ 15

–12 ≤ k ≤ 12

l range

-18 ≤ l ≤ 18

–15 ≤ l ≤ 16

–13 ≤ l ≤ 16

data/restraints/params

7853 / 0 / 425

3908 / 0 / 217

4296 / 0 / 280

GOF

0.890

0.842

0.859

R1, wR2[I>2σ(I)]a

0.0481, 0.1050

0.0462, 0.1091

0.0404, 0.1109

data]a

0.1240, 0.1397

0.1262, 0.1504

0.0673, 0.1323

0.404, -0.379

0.502, -0.334

0.487, -0.320

Dc μ

[g·cm–3]

[mm–1]

R1, wR2[all Δρmax, Δρmin [e·Å–3] 5 6

[a]

_

R1 = ||Fo| – |Fc||/|Fo|; wR2 = [[w (Fo2 – Fc2)2]/[ w (Fo2)2]]1/2.

Carbonization process of Metal–Organic Complexes

7

Subsequently, the three different MOC-1, MOC-2 and MOC-3 crystals materials

8

were heated to 900 °C and kept under 900 °C for 2 hours, the Zn metal was removed

9

by HF acid solution, obtained

N-doped porous carbon (NPCs) materials. The 9



Page 10 of 35

1

carbonization process and mechanism for NPCs is shown in Figure S5-S7 through the

2

corresponding picture and thermogravimetric analysis. The carbonization process is

3

divided into three stages, the first stage (0-270 °C), which can be attributed to the

4

mass loss of uncoordinated acetonitrile (CH3CN). The second stage (270-520 °C) is

5

due to the collapse of the skeleton together with the release of carbonaceous gas

6

products (mainly about C6H6, CO and CO2, CxHy hydrocarbon mixture) and ZnO.

7

The third stage of mass-loss started at 600 °C is due to further evaporation of CO2 and

8

CO through equation (1) and equation (2) as follows53,54:

9 10

ZnO + C → Zn (g) + CO

(1)

CO + O2 →CO2

(2)

11

After carbonization, the surface structures and crystallite morphology of these

12

MOCs precursors (Figure 4a-4c) shrinked and clearly displayed N-doped carbon

13

strctures, as presented in the Figure 4d-4f through photos and scanning electron

14

microscope (SEM). In addition, high-resolution transmission electron microscopy

15

(TEM) images (Figure 4j-4l) show that these NPCs are multi-walled with part of

16

crystal structure, and the lattice fringe of the interfacial distance is about 0.35 nm,

17

which can be attributed to the (002) crystal plane of the graphite carbon material

18

(Figure 5).55 Interestingly, the graphite layers in the NPC are not exactly parallel to

19

the same axis, but are oriented in different directions, thus exposing the rich edges

20

rather than the base on the surface of the NPCs, which would benefit for he enhanced

21

SO2 capture. From the selected area electron diffraction pattern (SAED), a typical

22

six-fold symmetrical peak is

shown, and the f2110g spot appears to be more intense 10


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1

than the f1100g spot, reflecting a high crystallinity of less than 5 layers.56,57

2 3

Figure 4. (a-c) Scanning electron microscope of MOC-1, MOC-2 and MOC-3 crystals. (d-f)

4

Photos of the N-doped porous carbon (NPCs) materials. (g-i) Scanning electron microscope

5

(SEM) and transmission electron microscopy (TEM) images of the NPCs.

6 7

Figure 5. Transmission electron microscopy (TEM) images of the NPC-1 and (b) NPC-2. 11



1

Characterization of the N-doped porous carbon

2

Nitrogen adsorption–desorption isotherms of the obtained NPCs are shown in

3

Figure 6a, which represents hierarchical pores with micropores and mesopores in

4

NPC-1, while dominant micropores in NPC-2 and NPC-3. Figure 6b represent the

5

pore size distribution and cumulative pore volume plots, obtained by the BJH

6

methods. All of them exisit high BET surface areas which are listed in Table S2, the

7

pore diameters are around 0.65 nm (Figure 6b). The BET surface area is 3186.5,

8

2252.1 and 2426.2 m2 g-1, respectively. Notably, the such high surface area, up to

9

3186.5 m2 g-1, which is one of the highest value for the reported carbons materials.54,58

10

Such microporous structure and high surface area is beneficial for SO2 adsorption.59

11

As we know, such high surface area has not been observed yet in any other type of

12

porous carbons, which is unique for MOCs derived porous carbon.27

13

The X-ray photoelectron spectroscopy (XPS) of the three NPCs were investigated

14

Figure 6c), which indicate that the NPCs are essentially a graphite-like structure, and

15

the type of carbon atom belongs to sp2 carbons. Two peaks around 284 and 399 eV in

16

the full scan spectra were attribution to C1s and N1s peaks, respectively, Zn 2p peak

17

is not detected in the XPS spectra. Table S3 listed the N and C content of the N-doped

18

porous carbon. Notably, the result of XPS and elemental analysis indicate that the

19

nitrogen content is 19.6%, 15.2% and 17.8%, respectively. High-resolution N 1s

20

spectra appeared at 401.2, 399.5, and 398.7eV are corresponding to graphitic-N,

21

pyrrole-N and pyridinic-N, respectively (as shown in Figure 6d).60,61 In addition,

22

oxygen contents occupied a small amount for these three NPCs, therefore, in 12


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1

subsequent studies, the oxygen content is not considered. Two peaks around 25° and

2

43° (Figure

3

(PXRD)), which were classified as (002) and (101) planes of the graphite type carbon

4

structure, indicating that the structure of three NPCs materials is essentially

5

disordered graphite-like carbon structure in nature. It serves to show that all N-doped

6

porous carbon materials exhibt broadened (002) peaks. Noteworthy, NPC-1 exhibits

7

the widest full width at half-maximum (FWHM)

8

N-content (17.8%) presents a FWHM of 11°, higher than that of 9° for NPC-2

9

(15.2%). According to the literature, the stacking height (Lc) is closely tied to FWHM

10

of (002) plane of graphitic structure (Lc = 0.89λ/(FWHM002cosθ002)), the larger of

11

FWHM, the more disordered stacks of carbon layers.62 Therefore, it is note that the

12

high N-doped will change sp2 C-stacking structure, which could be effect on the SO2

13

adsorption.

6e) of these three NPCs materials (powder X-ray diffraction patterns

of 12°, NPC-3 with higher

14

The Raman spectra of these three NPCs are shown in Figure 6f. Disordered

15

carbon (D-band) and graphitic carbon (G-band) appear in two different peaks around

16

1354 and 1593 cm-1, which is consistent with previous characterization results. The

17

data of ID/IG63 for NPC-1, NPC-1 and NPC-3 is 0.982, 0.976 and 0.981, respectively.

18

Notably, the data of ID/IG for NPC-3 is 0.981, which is higher than that of NPC-2

19

(0.976). Combination the results of Raman analysis and PXRD, it is found that N

20

atoms retained in the carbon lattice and high N-doped partially effect on the sp2

21

C-stacking structure

13



1 2

Figure 6. (a) Nitrogen adsorption-desorption isotherms of the obtained NPCs with data of BET

3

surface area (b) Pore volume values for the NPCs. (c) X-ray photoemission spectroscopy (XPS)

4

spectra in the full scan spectra of NPCs and (d) The high-resolution N 1s survey spectra of NPC-1.

5

(e) PXRD patterns and (f) Raman spectroscopy of the as-synthesized NPCs.

6

SO2 adsorption of N-doped porous carbon materials

7

Comprehensive analysis of the above results, these three N-doped porous carbons

8

with microporosity structure and different content of N are successfully synthesized. 14


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1

Benefiting from the above excellent characteristics, these three NPCs materials could

2

act as a good gas adsorbent for SO2 gas adsorption. Therefore, in this paper, we study

3

the gas adsorption behavior by using SO2 as a target molecule (Figure S8). As shown

4

in Figure 7a and 7b, the NPC-1 shows the highest SO2 adsorption (156.72 mg g-1),

5

which is one of the highest values of SO2 adsorption reported on carbon materials.

6

However, compared with the BET surface area and N-content of NPC-2 (2426.2 m2

7

g-1, 1.36 cm3 g−1, 15.2%) and NPC-3 (2252.1 m2 g-1, 1.46 cm3 g−1, 17.8%), SO2

8

adsorption capacity time and the breakthrough of NPC-3 (156.23 mg g-1) higher than

9

that of NPC-2 (112.86 mg g-1). Combination of the XPS, PXRD, Ranman results and

10

SO2 adsorption capacity, NPC-3 (17.8%), with higher nitrogen content and lower the

11

BET surface area presents higher SO2 adsorption capacity than that of NPC-2

12

(15.2%). These results indicate that high N-content plays a very critical role for

13

enhancing SO2 adsorption in the carbon materials.

14

Moreover, the cyclic adsorption performance of the NPCs adsorbents was tested.

15

NPCs adsorbents were treated by thermal regeneration (heated at 250 °C for 20 min),

16

after 10 cycles, SO2 adsorption capacity is almost the same, which demonstate that

17

their excellent cyclic adsorption performance, as shown in the Figure S9. As is

18

summarized in Figure 7c, compared with other types of carbon materials, SO2

19

adsorption capacity of these NPCs adsorbents is higher than that of others. In

20

addition, compared with other type of materials, such as zeolites,64,65 MOFs,66 and

21

ionic liquids,67 which are state of the art materials for SO2 adsorption, NPCs

22

adsorbents in this work also show higher SO2 adsorption capacity. 15



1 2

Figure 7. (a) The SO2 capture efficiencies and (b) Saturation uptake capacities of NPCs (25 ℃, 1

3

bar). (c) The amount of SO2 capture of the reported literatures and NPCs. (d) The SO2 removal

4

dynamics of selected NPC-1 under various gas compositions (the lines with symbols are the SO2

5

removal rate versus time; the line without symbols are the accumulation amount of SO2 uptake

6

versus time.

7

Based on the above analysis, we selected NPC-1 with the highest SO2 removal

8

capacity as a representative to study the influence of different gas compositions (eg.

9

N2, O2 and H2O) on SO2 adsorption behavior at 363K. On one hand (Figure 7d),

10

without any other gas addition, the separate SO2 adsorption rate drops sharply to

11

varying degrees until it drops to the lowest value. On the other hand, when N2 was

12

added (SO2 + N2), NPC-1 showed lower SO2 removal performance with SO2

13

adsorption of 7.2 mg g-1 and a saturation time of 25 minutes. When O2 (SO2 + O2) or

14

O2 and H2O (SO2 + O2 + H2O) are coexisted in the gas, the SO2 removal performance 16


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1

is greatly improved. The addition of O2 and H2O, respectively, can significantly

2

improve the adsorption performance of SO2. Simultaneous addition of O2 and H2O is

3

12 times more than the amount of SO2 adsorption without any gas, which is five times

4

that of the SO2 + O2 component. Simultaneous addition of O2 and H2O during SO2

5

adsorption significantly improves the SO2 removal performance. The SO2 removal

6

capacity is increased by more than 12 times compared to the case without any gas.

7

SO2 adsorption mechanism on theoretical level (int=ultrafine m062x)

8

As mentioned above, NPC-1 exhibits the highest SO2 adsorption due to the very

9

important factor of the highest N doping. To further study this behavior of NPCs, the

10

SO2 adsorption mechanism is carried out at the theoretical level (int=ultrafine

11

m062x).27,68-70 The SO2 adsorption mechanism of NPCs was studied by two model

12

with N-doped and without N-doped, as demonstrated in Figure 8a-8d. Theoretical

13

calculation analysis results (Figure 8e-8h) showed that the SO2 adsorption energy (Ed)

14

for the N-doped and un-doped graphite type carbon layer structure is -49.69 kJ/mol

15

and -36.22 kJ/mol, respectively, accounting for the higher SO2 adsorption energy for

16

N-doped model. That is to say, nitrogen doping greatly promotes the SO2 adsorption.

17

The theoretical study provides direction that the next-generation carbon materials can

18

be designed with high content of N for SO2 adsorption. Combined with the

19

electrostatic surface potential before and after SO2 adsorption and the local electron

20

density of LUMO and HOMO (Figure 8i-8p), it is shown that N-doped to graphite

21

carbon structure does change the internal structure. These effects may increase the

22

chances of SO2 interacting at the carbon edge position. Moreover, different adsorption 17



Page 18 of 35

1

positions (plane/edge) and adsorption patterns for SO2 adsorption were investigated,

2

density functional theory (DFT) calculations with the B3LYP exchange functional

3

employing 6-31G (d) basis sets using a suite of Gaussian 09 programs were

4

performed. Optimized structures, molecular orbital plots (LUMO and HOMO),

5

electron density distributions, electrostatic surface potential before and after SO2

6

adsorption were studied. Density-fitting approximations are used to accelerate

7

calculations and dispersion correction and geometric correction is considered. Single

8

point energy of these two with N-doped and without models are calculated and

9

followed by the adsorption energy (Ead) through the following equation (3) with

10

int=ultrafine m062x level: (3)

11

𝐸𝑎𝑑 = 𝐸𝑐𝑜𝑚𝑝𝑙𝑒𝑥 – 𝐸𝑆𝑂2 ― 𝐸𝑠𝑢𝑟𝑓𝑎𝑐𝑒

12

where 𝐸𝑆𝑂2, Esurface and Ecomplex express single point energies of conFigureuration

13

optimized SO2 molecule, the N-doped and without models before and after SO2

14

adsorption, respectively.

15

It is very interesting that the SO2 molecules are placed near the placement edge

16

and the basal plane when constructing the computational model. The calculation

17

results show the most important thing is that the geometric optimization of the SO2

18

molecule is adsorbed at the carbon edge rather than the surface region and is not

19

directly related to nitrogen atoms interact. That is to say, the adsorption of SO2

20

belongs to the adsorption of graphite carbon layer edges.

18


Page 19 of 35 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


1 2

Figure 8. (a-d) With N-doped and without N-doped carbon atoms saturated models for SO2

3

capture. (e-h) Electrostatic surface potential (i-p) Local electronic density of with N-doped and

4

without N-doped carbon atoms saturated models for SO2 capture. Top: The lowest unoccupied

5

molecular orbital (LUMO). Bottom: The highest occupied molecular orbital (HOMO).

6

 CONCLUSION

7

In this work, three different N-doped porous carbon materials (NPCs) with high

8

surface areas were successfully synthesized by carbonization of Metal–Organic

9

Complexe. The NPCs are sp2-bonded graphite carbon layer in nature. The NPCs show

10

one of the highest SO2 adsorption capacity over 156.72 mg g-1. It is found that SO2

11

adsorption capacity have a direct relationship with BET surface area and N-content: 19



Page 20 of 35

1

high BET surface area and N-content play a very critical role for enhancing SO2

2

adsorption. Finally, theoretical calculation demonstrate the fact that geometric

3

optimization of the SO2 molecule is adsorbed at the carbon edge rather than the

4

surface region or directly related to nitrogen atoms interact and

5

that the next-generation carbon materials can be designed with high content of N for

6

SO2 adsorption.

7

 EXPERIMENTAL SECTION

8

Synthesis of MOC-1

provides direction

9

A mixture of 6-methoxy-2-pyridinecarboxaldehyde (0.2 mL, 1.663 mmol),

10

p-aminobenzoic acid (228.1 mg, 1.663 mmol), ZnCl2 (227.2 mg, 1.663 mmol) were

11

dissolved in 25 mL CH3CN solution and constantly stirred for 1h, then heating reflux

12

for 12 h. After the reaction was completed, the resulting liquid was suction-filtered

13

with an oil pump to obtain pale yellow crystals. The crude product is recrystallized

14

from n-hexane to give a pale yellow solid. Anal. Calcd (%) for C30H27O6N5Cl4Zn2 (M

15

= 826.15 g mol−1): C, 43.61; H, 3.29; N, 8.48. Found: C, 43.60; H, 3.26; N, 8.46.

16

FT-IR (KBr, cm–1): 3543(w), 3426(w), 2939(w), 2529(w), 1687(s), 1605(s), 1578 (s),

17

1571(s), 1534(w), 1476(s), 1409(m), 1378 (m), 1359(m), 1322(w), 1291(s), 1240(m),

18

1184(m), 1098(w), 1086(w), 1101(s), 948(m), 868(m), 802(s), 734(m), 697(w),

19

671(m), 640(m), 577(m), 538(m), 518(w), 475(m), 437(w).

20

Synthesis of MOC-2

21

A mixture of 2-quinolinecarboxaldehye (196.6mg, 2 mmol), p-aminobenzoic

22

acid (274.3 mg, 2 mmol), ZnCl2 (273.2 mg, 2 mmol) were dissolving in 30 mL 20


Page 21 of 35 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


1

acetonitrile solutions and keeping stirring for 0.5h, subsequently, refluxing for 2 h.

2

The mixture was then cooled to room temperature and filtered with filter paper, then

3

volatilized while standing at room temperature. High transparent bulk single crystal

4

MOC-2 obtained after 2 days. Yield: 72%. Anal. Calcd (%) for C17H12O2N2Cl2Zn (M

5

= 776.07 g mol−1): C, 49.49; H, 2.93; N, 6.79. Found: C, 49.47; H, 2.92; N, 6.77.

6

FT-IR (KBr, cm–1): 3421(w), 3181(w), 1601(s), 1557(m), 1509(w), 1465(m),

7

1436(w), 1412(s), 1377(m), 1347(w), 1272(w), 1222(w), 1185(w), 1155(w), 1116(w),

8

965(w), 902(w), 853 (w), 801(m), 770(s), 637(m), 610(m), 521(m), 497(w), 436(m).

9

Synthesis of MOC-3

10

2-carboxaldehyde-1,10-phenanthroline (10.8 mg, 0.2 mmol), benzidine (36.8

11

mg, 0.2 mmol) and ZnCl2 (55.6 mg, 0.2 mmol) was added to the sealed vial, followed

12

by 15 mL CH3CN was added, all the mixture solution was stirred at room temperature

13

for 50 min and heated in an 85 °C oven for 1 day. A yellow block crystal of MOC-3

14

was obtained. Anal. Calcd (%) for C25H17N3Cl2Zn (M = 414.56 g mol−1): C, 60.57; H,

15

3.46; N, 8.48. Found: C, 60.56; H, 3.44; N, 8.46. FT-IR (KBr, cm–1): 3204(w),

16

2926(w), 1967(w), 1451(m), 1276(s), 1197(w), 1137(w), 1093(w), 1012(s), 985(m),

17

857(s), 840(s), 792(w), 748(s), 729(w), 709(m), 647(m), 635(w), 596(m), 553(w),

18

498(w), 484(w), 496(w), 445(m), 436(w).

19

Synthesis of N-doped porous carbon (NPCs)

20

The synthesized metal organic complex is uniformly placed into the quartz boat

21

as a precursor for preparing the carbon material. Then, the quartz boat was placed in a

22

programmed tube furnace having flowing N2 atmosphere for carbonization. The 21



1

furnace was heated to 900 °C at a heating rate of 10 °C min-1 and held at 900 °C for

2

2h. When the carbonization process stoped, the tube furnace was cooled naturally

3

with the black product in the quartz boat. The obtained crude product contained a

4

metal oxide, and the obtained black powder was stirred at 60 °C for 12 hours. The

5

metal oxide remaining in the crude product was washed with a 3 M HF solution (10

6

mL). The product was then separated from the mixed solution (filtered) and washed

7

with deionized water for several times and dried at 100 °C for 12 hours.

8

SO2 adsorption

9

The dynamic test of SO2 removal performance of nitrogen-doped microporous

10

carbon was carried out by using a fixed bed experimental system, and Figure S9

11

shows a schematic diagram of the entire test system. The fixed bed reactor was 20

12

mm in diameter and the glass reactor was placed vertically in a vertical tube furnace

13

with a valve and mass flow controller system. The Gasmet-DX4000 portable FTIR

14

emission gas analyzer from Finland was used to detect the concentration of

15

SO2/O2/H2O. 5 g of carbon material was supported on the sand core (120 mesh) of the

16

glass reactor before each SO2 adsorption test. After the reaction zone temperature

17

reached the set value, simulated flue gas (2000 ppm SO2 with or without 5% O2, with

18

or without 10% H2O, total flow of 1.5 L/min, with nitrogen balance) was introduced.

19

The water vapor was introduced through a water bath through a certain amount of N2,

20

and the amount of water vapor in the simulated flue gas was controlled by controlling

21

the flow rate of the nitrogen gas. The SO2 concentration at the inlet and outlet was

22

recorded by flue gas analyzer in real time, and the relationship between SO2 removal 22


Page 22 of 35

Page 23 of 35 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


1

efficiency and rate versus time was further processed recorded by the flue gas

2

analyzer. The SO2 removal performance of the nitrogen-doped microporous carbon

3

was calculated by integrating the desulfurization curve with the area above the

4

reaction time.

5

Theoretical calculation

6

Theoretical calculation (Int=ultrafine m062x) were carried out in Gaussian 09

7

software. The geometries Optimized structures, molecular orbital plots (LUMO and

8

HOMO), electron density distributions, electrostatic surface potential before and after

9

SO2 adsorption characterized at B3LYP/6-31G (d, p) level. Single point energy of

10

these two with N-doped and without models are calculated and followd by the

11

obtation of adsorption energy (Ead) through the following equation (2) with

12

int=ultrafine m062x level: 𝐸𝑎𝑑 = 𝐸𝑐𝑜𝑚𝑝𝑙𝑒𝑥 – 𝐸𝑆𝑂2 ― 𝐸𝑠𝑢𝑟𝑓𝑎𝑐𝑒where 𝐸𝑆𝑂2, Esurface and

13

Ecomplex express single point energies of optimized SO2 molecule, the N-doped and

14

without models before and after SO2 adsorption, respectively.

15



16

Supporting Information

17

The Supporting Information is available free of charge on the ACS Publications

18

website at http://pubs.acs.org: Selected bond distances and angles for MOC-1, MOC-2

19

and MOC-3. Crystal structures of MOC-1, MOC-2 and MOC-3. Elemental contents of

20

the different graphite type nano-sheets porous carbon NPCs by elemental analysis and

21

XPS. BET surface areas, pore volumes and pore sizes of N-doped porous carbons

22

materials NPCs. Carbonization mechanism and process for porous carbons NPCs.

ASSOCIATED CONTENT

23



Page 24 of 35

1



2

The authors declare no competing financial interest.

3



4

This work was supported by National Natural Science Foundation of China

5

(Grant No. 21873025, 21571042 and 51603055).

6



7

(1) Adil, K.; Belmabkhout, Y.; Pillai, R. S.; Cadiau, A.; Bhatt, P. M.; Assen, A. H.;

8

Maurin, G.; Eddaoudi, M., Gas/vapour Separation Using Ultra-microporous

9

Metal-organic Frameworks: Insights into the Structure/separation Relationship. Chem.

CONFICT OF INTEREST

ACKNOWLEDGEMENTS

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1

Table of Contents Use Only

2

N-doped Porous Carbon Derived by Direct Carbonization of Metal–Organic

3

Complexes Crystal Materials for SO2 Adsorption

4

Ani Wang,a Ruiqing Fan,*,a Xinxin Pi,b Sue Hao,a Xubin Zhenga and Yulin Yang*,a

5 6

N-doped microporous carbon (NPCs) materials with high BET surface area have been

7

synthesized from carbonization of imine-based Metal–Organic Complexes (MOCs) for SO2

8

adsorption.

9

35


N-doped Porous Carbon Derived by Direct Carbonization of Metal

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