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N-doped ordered mesoporous carbon originated from a green biological dye for electrochemical sensing and high pressure CO2 storage Shenghai Zhou, Hongbo Xu, Qunhui Yuan, Hangjia Shen, Xuefeng Zhu, Yi Liu, and Wei Gan ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.5b10502 • Publication Date (Web): 10 Dec 2015 Downloaded from http://pubs.acs.org on December 16, 2015

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ACS Applied Materials & Interfaces

N-doped ordered mesoporous carbon originated from a green biological dye for electrochemical sensing and high pressure CO2 storage

Shenghai Zhou a, Hongbo Xu a,b, Qunhui Yuan a,*, Hangjia Shen a,b, Xuefeng Zhu a, Yi Liu c,*, Wei Gan a,*

a

Laboratory of Environmental Science and Technology, Xinjiang Technical Institute

of Physics & Chemistry; Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011, China b

c

University of Chinese Academy of Sciences, Beijing 100049, China

The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley,

California, 94720, USA.

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ABSTRACT: Herein, a series of nitrogen-doped ordered mesoporous carbons (NOMCs) with tunable porous structure were synthesized via a hard-template method with a green biological dye as precursor, under various carbonization temperatures (700–1100 °C). unmodified

Compared with the ordered mesoporous silica modified and the

electrodes,

the

use

of

electrodes

coated

by

NOMCs

(NOMC-700–NOMC-1100) resulted in enhanced signals and well-resolved oxidation peaks in electrocatalytic sensing of catechol and hydroquinone isomers, attributable to NOMCs’ open porous structures and increased edge-plane defect sites on the N-doped carbon skeleton. Electrochemical sensors using NOMC-1000 modified electrode were fabricated and proved feasible in tap water sample analyses. The NOMCs were also used as sorbents for high pressure CO2 storage. The NOMC with the highest N content exhibits the best CO2 absorption capacities of 800.8 mg/g and 387.6 mg/g at 273 K and 298 K (30 bar), respectively, which is better than those of other NOMC materials and some recently reported CO2 sorbents with well-ordered three-dimensional porous structures. Moreover, this NOMC shows higher affinity for CO2 than N2, benefited from its higher nitrogen contents in the porous carbon framework.

KEYWORDS: nitrogen-doped ordered mesoporous carbons; biological dye; electrochemical sensor; catechol and hydroquinone; high pressure CO2 storage 2 ACS Paragon Plus Environment

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INTRODUCTION

Carbon nanomaterials have attracted considerable attention in electrocatalysis and electrochemical

sensing

because

of

their

high

catalytic

activities,

wide

electrochemical potential windows, good biocompatibilities, and low costs.1 Various carbon nanomaterials, such as graphene (GR),2,3 carbon nanotube (CNT),4,5 carbon nanofiber,6 carbon nanopolyhedron7 and ordered mesoporous carbon (OMC),8,9 have been developed and used as electrode materials for electrochemical analyses of inorganic, organic and biologic species. Among these carbon materials, OMC is an efficient electrode material that combines the advantages of carbon and ordered mesoporous materials. The carbon nature provides good conductivity, decent chemical stability, and high electrocatalytic activity, while its ordered mesoporous architecture offers high specific surface area and open pores that lead to amplified target/receptor interfaces and fast diffusion path for analyte.10-14 For example, as reported by Zhou et al.15 and Wang et al.,16 OMCs show improved electrocatalytic activities compared with CNTs and GR in the electrochemical oxidation sensing of glutathione, norepinephrine, dopamine, hydrogen peroxide, and so on. Our previous studies have also demonstrated that ordered nanoporous carbons derived from metal-organic frameworks that contain abundant electroactive graphene fragments and ordered open pores can remarkably improve the efficiency in electrochemical detection of Pb(II) and Cd(II).17,18



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Recently, nitrogen-doped carbons have attracted growing interests because of their improved

electrocatalytic activities compared

with those

of carbonaceous

materials,19-22 thus expanding their applications in the fields of electrocatalysis and electrochemical sensing.23,24 Therefore, great effort has been made to prepare various nitrogen-doped carbons, among which nitrogen-doped OMCs (NOMCs) is one of the most promising types for their enhanced electrocatalytic properties.25-27 NOMCs are also considered as attractive materials in greenhouse gas CO2 capture and storage due to their intriguing features such as good chemical and thermal stability, designable and open pore structure as well as abundant basic adsorption site.28,29 For example, Wei et al. reported a controllable synthesis of rich nitrogen-doped OMCs for CO2 capture.30 The NOMCs show excellent performance as absorbents for CO2 capture (2.8-3.2 mmol g−1, 298 K, 1.0 bar). Yu et al. demonstrated an one-pot synthesis of highly ordered nitrogen-containing mesoporous carbon with resorcinol-urea-formaldehyde resin for CO2 capture via a soft-templating strategy.31 The presence of nitrogen groups significantly improved the CO2 adsorption capacity (3.3 mmol g−1 at 273 K, 2.6 mmol g−1 at 298 K) compared with the un-doped ones with comparably high surface areas. Considering popularity of the CO2 adsorption process based on pressure-swing adsorption (PSA) units where adsorption and desorption of CO2 takes place under relatively large pressure fluctuations,32 a novel kind of NOMC has recently been used as sorbent for high pressure CO2 capture and storage by Lakhi et al.28 However, to the best of our knowledge, the study on design 4 ACS Paragon Plus Environment

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and application of efficient NOMC adsorbents with high capacities at high pressures is still very limited. In general, three approaches are used for the preparations of nitrogen-doping of ordered mesoporous carbons: the soft-template method,30,31 the post-treatment strategy,33 and the hard-template method.25,27 Recent studies show that the hard-template method is prevalent in fabricating NOMC, due to its advantages of giving more robust NOMC structure, controllable distribution of N dopant and less poisonous operational atmosphere than the post-treatment strategy.25,33-35 Besides, it usually gives higher N-doping amount and surface area compared with the soft-template method.29, 30, 36, 37 Using ordered mesoporous silica (SBA-15,35 KIT-6,38 and FDU-12,28 etc.) as hard templates and nitrogen-containing precursors (honey,25 cyanamide,35 melamine,38 ethylenediamine,28 diaminobenzene,39 and gelatine,40 etc.) as N dopants, some novel kinds of NOMCs have lately been developed. Nevertheless, considering the wide usages in electrocatalysis/electroanalysis and high pressure CO2 storage of the NOMC materials, preparation of NOMCs with commonly available, less expensive and greener precursors is still highly desirable. In this study, we demonstrate a green and controllable synthesis of a series of NOMCs using ethyl violet, a commercially available and low-toxicity biological dye, as both the carbon and nitrogen sources. Ordered mesoporous SBA-15 silica was used as the hard template. The obtained NOMCs with tunable microstructures and N-contents were used for the simultaneous electrocatalytic sensing of catechol (CC) 5 ACS Paragon Plus Environment


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and hydroquinone (HQ), which commonly coexist in the environment as phenolic contaminants.41 The NOMCs exhibited notably improved electrocatalytic activities for distinguishing CC from the interferential HQ compared with bare glassy carbon electrodes (GCEs). The effect of porous structure and N-content of the NOMCs on the electrocatalysis performance was systematically discussed. The possibility of application of the NOMC in real water analyses for detection of CC in the presence of HQ was evaluated. Moreover, the CO2 uptake capacities at high pressure are tested for these NOMC obtained under various conditions, among which the NOMC with the highest N content showed a high adsorption capacity and a good selectivity towards CO2. EXPERIMENTAL SECTION

Reagents and Apparatus. All chemicals were of analytical grade and used as received. Pluronic P123 triblock copolymer (EO20PO70EO20, EO = ethylene oxide, PO = propylene oxide) was purchased from Aldrich. Tetraethylorthosilicate (TEOS) was purchased from Alfa. Ethyl violet was purchased from TCI. Catechol (CC), hydroquinone (HQ), sulfuric acid and hydrochloric acid were obtained from Beijing Chemical Plant. Deionized water (DI water, 18.25 MΩ·cm) was prepared from a water purifier (WP-UP-UV-20, Sichuan water technology development Co. Ltd, China). Transmission electron microscopy (TEM) images were recorded on a JEOL JEM-3010 transmission electron microscope. Scanning electron microscopy (SEM) and SEM/energy dispersive spectroscopy (EDS) images were collected on a Zeiss 6 ACS Paragon Plus Environment

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Supra-55 field-emission scanning electron microscope. X-ray photoelectron spectroscopy (XPS) experiments were performed using an Al Kα source at room temperature. Nitrogen adsorption–desorption experiments were performed on a N2 adsorption apparatus (Quantachrome Instruments, USA). Low-angle powder X-ray diffraction (XRD) was carried out with an X-ray diffractometer (D8, Bruker Germany). The electrochemical experiments were carried out in a conventional three-electrode cell controlled by a CHI 660E electrochemical workstation (Chenhua Instrument, Shanghai, China). The NOMC-modified electrode was used as the working electrode. A platinum wire was used as the counter electrode and a saturated calomel electrode (SCE) served as the reference electrode. All of the potential values given below are with respect to the SCE. The high pressure N2 and CO2 adsorption were performed by HPVA-200 of Micromeritics (USA). Synthesis of SBA-15. SBA-15 was synthesized based on a method that was used in a previous report and our work.42,43 Firstly, 4 g P123, 20 mL HCl (37%) and 8.5 g TEOS were dissolved in 105 mL H2O. The resulting solution was then allowed to react at 110 °C for 24 h. The final product was retrieved by washing with deionized water and ethanol in sequence, dried at 60 °C overnight, and then calcinated at 550 °C for 5 h to obtain the white SBA-15 powder. Preparation of the NOMCs. The synthesis route of NOMC is shown in Figure 1. Briefly, the obtained SBA-15 was impregnated with a solution containing 0.65 g ethyl violet and 40 µL sulfuric acid. The resulting mixture was then sequentially heated at 7 ACS Paragon Plus Environment


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100 °C for 6 h and at 160 °C for another 6 h. The obtained composite was then calcined at different target temperatures ranging from 700 to 1100 °C to obtain a black powder. Finally, the obtained black powder was washed with hydrofluoric acid to remove the SBA-15 template. The obtained samples are denoted as NOMC-x, where x represents the carbonization temperature, i.e., x = 700, 800, 900, 1000, or 1100.

Figure 1. Schematic diagram of the preparation of the NOMC. Preparation of the SBA-15 and NOMC-x modified electrode. To prepare the SBA-15 and NOMC-x modified GCE, the bare GCE was polished with 0.3- and 0.05-µm alumina slurries, and then cleaned by ultrasonication in DI water and ethanol. The SBA-15 modified electrode (denoted as SBA-15/GCE) GCE was prepared by casting 5 µL SBA-15-DMF suspension of 1 mg/mL onto a clean GCE surface and drying for 30 min under an infrared lamp. A similar procedure was performed for the NOMC-x modified electrode, except that SBA-15 was replaced by NOMC-x (denoted as NOMC-x/GCE). 8 ACS Paragon Plus Environment

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RESULTS AND DISCUSSION Structural and morphological characterizations of NOMCs. The pore structural order of the obtained NOMCs has been characterized by low-angle XRD since it is commonly used for the discrimination of well-ordered mesoporous silica and carbon materials.15,42,44 The low-angle XRD pattern of SBA-15 template in Figure 2 exhibited three well-resolved peaks, which could be assigned to the (100), (110), and (200) reflections, indicating the ordered two-dimensional hexagonal p6mm symmetry of the SBA-15.45 Similar to the parent SBA-15 template, the low-angle XRD patterns of all NOMCs displayed three featured peaks at similar positions, suggesting that the structural order was maintained after the removal of SBA-15 template39 and confirming the feasibility of using ethyl violet as a green precursor. Besides, the d-spacing value ratios of the three reflections of all NOMCs possess the same value of 1:(1/√3):(1/2) as that of the SBA-15 template, suggesting the existence of the (100), (110), and (200) reflections of the ordered two-dimensional hexagonal mesoporous structures (p6mm).45 It is also noteworthy that at increased temperatures (700→1100°C), the three corresponding diffraction peaks of NOMC shifted to higher angle, implying the decreased pore size of the NOMC. The shrinkage of pores in the NOMCs should result from the shrunk framework of the SBA-15 template, which was caused by carbonization at the increased temperatures. However, the thermally stable mesoporous structure of all NOMCs is still maintained. The lattice parameters (a0) deduced from the (100)



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reflections are 11.2, 10.2, 10.1, 9.9, 9.8 and 9.6 nm for SBA-15, NOMC-700, NOMC-800, NOMC-900, NOMC-1000, NOMC-1100, respectively. The marginal changes of lattice parameters at different temperatures indicate the existence of thermally stable mesostructure.46 The intensities of diffraction peaks of SBA-15 and NOMCs were also compared. It is noticed in Figure 2 that all three peaks, especially the (110) and (200) reflections, became weakened after calcination, suggesting a reduction of the structural ordering of NOMCs during the carbonization and removal of silica template in HF.39 Among all of NOMCs, NOMC-900 possesses an XRD pattern with relatively higher intensities than other NOMC-x, indicating a better mesostructural regularity of the obtained NOMC-900.25 When higher carbonization temperature (＞900°C) was applied, the intensities of the diffraction peaks at small angles were weakened, implying the degradation of mesostructural regularity of the NOMCs at higher temperature, consistent with prior observations reported by Chen et al.29


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Figure 2. Low-angle XRD patterns of SBA-15 and NOMCs (from bottom to top: SBA-15, NOMC-700, NOMC-800, NOMC-900, NOMC-1000, NOMC-1100). N2 adsorption–desorption was used for the characterization of the pore structures of SBA-15 and NOMCs. Figure 3A depicts the N2 adsorption-desorption isotherms of the obtained materials. All of the isotherms exhibited the type IV features with H1 hysteresis loops corresponding to capillary condensation of nitrogen in the mesopores,40,45 indicating the presence of well-ordered mesopores in both SBA-15 and its carbon replicas. This result agrees well with the data obtained from the low-angle XRD characterization, as detailed in Figure 2. Besides, the hysteresis loops of the NOMCs were observed at lower relative pressure than that of the SBA-15 template, suggesting that the NOMCs possess smaller mesopores than their parent SBA-15 template.47 This speculation is also consistent with the pore size distributions of SBA-15 and NOMCs (Figure 3B), which are calculated based on their desorption curves with the Barrett–Joyner–Halenda method. The detailed pore sizes, Brunauer–Emmett–Teller (BET) surface areas, pore volumes, and microporous and mesoporous pore volume parameters of NOMCs were summarized in Table 1. Compared with the SBA-15 template which bears relatively large mesopores at a size around 6.56 nm, the NOMCs have smaller mesopores, with sizes decreasing from 3.71 to 3.32 nm as the carbonization temperature increases. Meanwhile, the surface areas (831.96–1430.84 m2/g) and pore volumes (1.38–2.14 cm3/g) of the NOMCs are also found to be tunable by varying the pyrolysis temperature from 700 to 1100 °C, 11 ACS Paragon Plus Environment


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with the largest surface area (1430.84 m2/g) and pore volume (2.14 cm3/g) achieved under 900 °C calcination. It is also noteworthy that a pore texture with the majority of mesopores was deduced as shown in Table 1. Similar to some previous reports,25,44 the control of pyrolysis temperatures was also proved to be effective for the adjustment of surface areas and pore volumes of the templated ordered mesoporous carbon in this work. However, to the best of our knowledge, the detailed reasons that lead to the variable pore textural parameters of OMC via controlling pyrolysis temperatures is still an unsolved mystery now.

Figure 3. (A) N2 adsorption–desorption isotherms and (B) pore size distributions of SBA-15 and NOMCs. Table 1. Textual parameters and N-doping contents of NOMC-x.

Sample

BET surface

Pore diameter

Pore volume

Meso-PV

Micro-PV

N-content

area (m2/g)

(nm)

(PV, m3/g)

(PV, m3/g)

(PV, m3/g)

(wt%)

NOMC-700

958.75

3.71

1.49

1.16

0.33

12.93

NOMC-800

831.96

3.54

1.38

1.04

0.34

8.94

NOMC-900

1430.84

3.34

2.14

1.71

0.43

5.79

NOMC-1000

1100.92

3.32

1.41

1.03

0.38

5.63

NOMC-1100

1097.49

3.32

1.61

1.19

0.42

4.83


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The morphology and microstructures of the NOMCs were also investigated by scanning electron microscopy and transmission electron microscopy. As shown in Figure 4B–F, the as-synthesized NOMC-x sample show a rod-like morphology similar to that of SBA-15 (Figure 4A), indicating the successful structural replication (inversely) of the parent template.25 There is no distinguishable morphological difference for all of NOMCs, suggesting that carbonization temperature has only minor effect on the morphology of NOMC nanoparticles. The TEM images in Figure 5B–F show all parallel black-and-white strips pattern, in which the black strips represent the carbon nanorod while the white ones are the hollow mesopores of NOMC. These parallel white strips, a linear array of mesopores derived from SiO2, also indicate a successful inverse replica of mesoporous silica of SBA-15 with 2D hexagonal arrangement (Figure 5A).39

Figure 4. SEM images of NOMC-x and SBA-15 (A-F: SBA-15, NOMC-700, NOMC-800, NOMC-900, NOMC-1000, NOMC-1100).



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Figure 5. TEM images of NOMC-x and SBA-15 (A-F: SBA-15, NOMC-700, NOMC-800, NOMC-900, NOMC-1000, NOMC-1100). The N-doped contents in all of the NOMCs were evaluated by the SEM/EDS technique. As shown in Table 1, the N-content reached a maximum (12.93 wt%) at a pyrolysis temperature of 700 °C and gradually decreased with increasing carbonization temperature. A similar trend of N-content at different temperatures has been previously reported.35,44 The chemical states of N in the NOMCs were further analyzed by X-ray photoelectron spectroscopy (XPS). The high-resolution N 1s XPS spectra shown in Figure 6 could be deconvoluted into three peaks with binding energies centered at 398.2, 399.7, and 400.9 eV, which correspond to the presence of pyridinic N, pyrrolic N, and quaternary N, respectively.48 The discovery of pyridinic N and pyrrolic N in the carbon matrixes, along with the high surface areas and abundant pores, indicates that the present NOMCs are promising electrodes components for electrocatalysis


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considering the expedient diffusion of analyte and enlarged electrochemically active surfaces in the presence of pyridinic N and pyrrolic N.35

Figure 6.

High-resolution N 1s XPS spectra of NOMC-x (from bottom to top:

NOMC-700, NOMC-800, NOMC-900, NOMC-1000, NOMC-1100). We compared the as-prepared NOMCs with the NOMCs obtained from other N-containing carbon precursors via similar thermal treatments. The present NOMCs exhibit comparable or better characteristics in terms of high surface area, large pore volume, high N-content, as shown in Table S1. Electrochemical application of NOMC-x Electrocatalytic discrimination of coexisting isomers CC and HQ The as-prepared NOMCs were applied as electrode modifiers for the electrocatalytic discrimination of the coexisting isomers CC and HQ. CC is a highly toxic and low degradable phenolic pollutant in the environment, and has received considerable attention in the field of environmental pollutant analysis.49-52 The 15 ACS Paragon Plus Environment


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development of novel materials and new strategies to monitor CC has thus become an area

of

interest.49,50 Compared

spectrophotometry,51

gas

with

other

analytical

chromatography–mass

methods

such

spectrometry,52

as and

high-performance liquid chromatography,53 the electrochemical approach is of great interest because of its simplicity, high sensitivity, fast response, and low cost.2,54 Efficient catalytic electrode materials are a prerequisite for selective detection of CC at an electrode due to the overlap of the oxidation peaks of CC and its interferential isomer HQ.41,55 It has recently been reported that some novel nanomaterials, such as gold nanocubes, graphene nanosheets and carbon nanotubes can be used for the electrochemical sensing of CC.50,56,57 Compared with the bare GCE, enhanced catalytic activity for sensing could be achieved with the combination of these materials due to increased active surface area. The as-prepared NOMCs with high surface areas, abundant edge-plane defects and doped nitrogen contents may also be suitable as catalytically active electrode materials, resulting in enhanced electrocatalysis and sensing performance in discriminating coexisting CC and HQ. Here, the electrocatalytic sensing was evaluated by differential pulse voltammetric (DPV) methods. Figure 7A shows the DPV responses to a mixture of CC and HQ at different electrodes:

NOMC-700/GCE,

NOMC-800/GCE,

NOMC-900/GCE,

NOMC-1000/GCE, NOMC-1100/GCE, SBA-15/GCE, and unmodified GCE. With 16 ACS Paragon Plus Environment

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the unmodified GCE, only a broad anodic peak is observed, in accordance with less amount of reactive sites available.41,55 Similar to the unmodified GCE, a single peak is observed at the SBA-15/GCE, suggesting that electrochemically inert silica cannot differentiate the two isomers even though it contains ordered mesopores. When NOMCs are employed, two well-resolved peaks that correspond to the oxidation of HQ (ca. +0.04 V) and CC (ca. +0.15 V), respectively, are observed, indicating the remarkably enhanced electrocatalytic sensing ability at the NOMC-x/GCEs. Figure 7B shows that NOMC-1000 exhibits the highest electrochemical response among all the NOMC materials tested. This result is somewhat counter-intuitive because the porous modifier with higher surface area and larger nitrogen contents is expected to have higher electrocatalytic activity. It suggests that factors other than surface area and nitrogen contents, such as porosities, surface states and porous structures of the modifiers, may also affect the electrochemical properties of the modified electrodes.58,59 Based on this measurement, the NOMC-1000 was selected as the sensing material for selective determination of CC in further experiments.



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Figure 7. (A) DPV response to a mixture of 0.06 mM HQ and 0.06 mM CC in 0.1 M PBS (pH=7.4) at bare GCE, SBA-15/GCE, and NOMC-x/GCE. (B) Oxidation currents of CC at NOMC-x/GCE (x = 700, 800, 900, 1000, and 1100). Electrochemical redox behavior of CC at NOMC-1000/GCE The electrochemical redox behavior of 1×10-4 mol L-1 CC at NOMC-1000/GCE was further investigated by cyclic voltammetry in a pH range of 5.9 to 8.0. It can be seen in Figure 8A that the peak potential shifted negatively with the increase of the pH value, indicating the participation of protons in the electrochemical redox process.56 As shown in Figure 8B, both the anodic peak potential (Epa) and the cathodic peak (Epc) of CC were found to be proportional to the pH value ranging from 5.9

to

8.0,

and

follow

be Epa (V) = 0.6006 − 0.0596*pH

the

following

(R = 0.999)

linear

regression

equations

and Epc (V) = 0.5498 − 0.0587*pH

(R = 0.999) for the oxidation and reduction process, respectively. Each slope in the above equations is very close to the theoretical value of 0.059 V pH-1 for 2-electron and 2-proton reactions, suggesting that the electrochemical redox reaction of CC at NOMC-1000/GCE follows a route involving two electrons and two protons.55 The probable electrochemical reaction of CC at NOMC-1000/GCE was described in Figure 8C. Moreover, the relationship between pH and the oxidation peak current was also investigated at the NOMC-1000/GCE (Figure 8D). The oxidation peak current of CC increases gradually with the pH value increases from 5.9 to 7.4, then sharply


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decreases as the pH value changes from 7.4 to 8.0. Therefore, the pH value of 7.4 was selected as the optimum pH value in the following electrochemical experiments.

Figure 8. (A) CVs of 0.1 mM CC in phosphate buffer solutions at different pH from 5.9 to 8.0 at NOMC-1000/GCE; (B) The dependence of Epa (Epc) of CC on the pH values; (C) Redox equation of CC at NOMC-1000/GCE; (D) The dependence of Ipa of CC on the pH value.

Selective detection of CC in the presence of HQ To determine the concentration range for the selective detection of CC in the presence of HQ, DPV measurements were carried out by changing the concentrations of CC while the concentration of HQ being kept constant. As shown in Figure 9, the oxidation current of CC at NOMC-1000/GCE was proportional to its concentration,



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while the DPV signals of HQ barely changed. The linear regression equation is Ip = 0.26*CCC − 0.23 (Figure 9B, R=0.997). The detection limit at NOMC-1000/GCE was estimated to be 0.9 µM (at a signal-to-noise ratio of 3), which is comparable to those of some other electrodes such as GR-PDA/GCE,60 CNT-TiO2/GCE,61 and GR-CNT/GCE.62 The calibration curve covers a wider range (6–70 µM) than GR-BMIMPF6/GCE,56 CNT-IL-Gel/GCE,57 and OMC-Nafion/GCE,63 suggesting that NOMC-1000 is promising for the fabrication of highly efficient electrochemical sensors for CC. The sensitivity for the detection of CC in the absence of HQ was also measured (data not shown here). The slope of the calibration curve was determined to be 0.22 µA/µM, which is close to the value of 0.26 µA/µM obtained in the presence of HQ. The stability of the NOMC-1000/GCE after two weeks storage at 4 ºC was evaluated by testing three electrodes prepared in the same way. The oxidation current responses to 20 µM catechol remained 95.1–97.4% of their initial values after storage, indicating a good stability of the present NOMC-1000/GCE. The reproducibility of the NOMC-1000/GCE was also estimated based on three independent electrodes. The results for the determination of 20 µM catechol indicate a good reproducibility of the present NOMC-1000/GCE, with a relative standard deviation (RSD) value of 7.8%. To evaluate the practical application of the fabricated NOMC-1000/GCE, it was used for the determination of CC in tap water samples. The standard addition method was used by spiking known amounts of analytes into the samples, because the 20 ACS Paragon Plus Environment

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original amount of CC in tap water is low. The results in Table 2 show that satisfactory recoveries were obtained for the determination of CC in the presence of 40 µM HQ, indicating the feasibility of the proposed NOMC-1000/GCE in selective determination of dihydroxybenzene contamination in real environmental samples.

Figure 9. (A) DPVs at NOMC-1000/GCE in 0.1 M PBS (pH 7.4) containing 40 µM HQ and different concentrations of CC (6, 10, 20, 30, 40, 50, 60, 70, 80, and 90 µM). (B) Oxidative peak current (ip) versus concentration of CC. Table 2. Results of selective determination of CC in the presence of 40 µM HQ in tap water samples (each sample was tested for three times). Sample

Added (µM)

Found (µM)

Recovery (%)

RSD (%)

1

10

10.1 ± 0.8

101.0

8.1

2

40

36.2 ± 1.6

90.5

4.6

High pressure CO2 storage The CO2 adsorption isotherms of various as-prepared NOMC materials were also investigated at 298 K under high pressure and compared in the Figure 10A. It is 21 ACS Paragon Plus Environment


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shown that the NOMC-700 with highest N content (12.93 wt%) displays larger sorption capacity than other NOMC materials at 30 bar, although it has a relatively low surface area of 958.7 m2/g. The measured uptake capacity for NOMC-700, NOMC-800, NOMC-900, NOMC-1000 and NOMC-1100 is 387.6, 365.6, 311.7, 214.2 and 274.3 mg/g at 30 bar, respectively. This trend indicates that the increased nitrogen functionalities incorporated into NOMC-x may be the dominant factor for the uptake of CO2, as has also been pointed out in previous reports.64,65 The uptake of N2 with NOMC-700 under the similar conditions was also investigated and the result was shown in Figure 10B. It was found that the N2 adsorption capacity of NOMC-700 at 30 bars is about 73.6 mg/g, which is about five-times lower than that for CO2 adsorption. The adsorption isotherms in Figure 10B also suggest that NOMC-700 exhibits a higher affinity for CO2 than N2 at both low and high pressures.

Figure 10. (A) CO2 adsorption isotherms of NOMC materials (NOMC-700, NOMC-800, NOMC-900, NOMC-1000, NOMC-1100) at 298 K; (B) CO2 adsorption isotherms of NOMC-700 at 273 K and 298 K and N2 adsorption isotherm for NOMC-700 at 298 K. 22 ACS Paragon Plus Environment

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It is known that the quantity of CO2 adsorption is strongly dependent on the temperature.28 Therefore, as a comparison, the high-pressure CO2 adsorption capacity of NOMC-700 at a relatively low temperature (273 K) was also measured and plotted in Figure 10B. NOMC-700 showed higher CO2 adsorption capacity (800 mg/g) at 273 K. Besides, the isotherm is far from saturation under this condition (273 K, 30 bar), indicating that the NOMC-700 may accommodate more CO2 at even higher pressures and lower temperatures. A comparison of CO2 uptake capacities of NOMC with other relevant materials is presented in Table S2. Under same experimental conditions, the as-prepared NOMC-700 shows higher CO2 storage capacity than a range of known porous mateirals, such as mesoporous alumina, γ-Alumina, mesoporous silica SBA-15, microporous zeolite 13x and well-ordered three-dimensional (3D) porous carbon nitrides.28,66 CONCLUSIONS A series of nitrogen-rich ordered mesoporous carbons were successfully synthesized by a hard-template method with the use of a low-toxic carbon/nitrogen precursor. The synthesized NOMCs exhibit favorable characteristics of high surface area, large pore volume and high N-content. The NOMCs show excellent sensing ability for dihydroxybenzene isomers (CC and HQ) because of their open pores, large surface areas, and abundant edge-defect sites, which ensure the easy access and reaction of target analytes. The electrocatalytic performance of the NOMCs can be adjusted by tuning the carbonization temperature. A NOMC-based electrochemical sensor for selective determination of CC in real water samples was also fabricated.



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The capacity of the NOMC materials for CO2 capture and storage was also investigated. The NOMC with the highest N content (NOMC-700) displays the largest sorption capacity among all the NOMCs. It also shows better capacity than some previously reported 3D porous adsorbents, such as mesoporous alumina, γ-Alumina, mesoporous silica SBA-15, microporous zeolite 13x and mesoporous carbon nitrides. Taking together, the NOMCs are proved as a class of multifunctional materials with tunable porous parameters and surface states, which may find further applications in areas such as catalyst support, supercapacitor, and lithium–sulfur battery. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected], [email protected] and [email protected]

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT S.H.Z. thanks the financial support from the ‘Western Light Program’ of the Chinese Academy of Sciences (XBBS201317) and the ‘International Science and Technology Cooperation Project (20146003)’ of the Xinjiang Uyghur Autonomous Region. Q.H.Y. and W.G. acknowledge the support from the ‘One Hundred Talents Project Foundation Program’ of the Chinese Academy of Sciences, the National Natural Science Foundation of China (21203244, 21473247) and the ‘Young Creative Sci-Tech Talents Cultivation Project’ of the Xinjiang Uyghur Autonomous Region.


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Y.L. thanks the support from the Molecular Foundry, which is supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. SUPPORTING INFORMATION. Comparison of textual parameters and N-doping contents of the NOMCs prepared with ethyl violet and some other N-containing carbon precursors via hard template method; CO2 capture capacities of adsorption of sorbent



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