Boron Nitride Mesoporous Nanowires with Doped Oxygen Atoms for

Research Article pubs.acs.org/journal/ascecg

Boron Nitride Mesoporous Nanowires with Doped Oxygen Atoms for the Remarkable Adsorption Desulfurization Performance from Fuels Jun Xiong,† Lei Yang,‡ Yanhong Chao,‡ Jingyu Pang,‡ Ming Zhang,† Wenshuai Zhu,*,‡ and Huaming Li*,† †

Insititute for Energy Research, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, PR China School of Chemistry and Chemical Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, PR China

‡

ABSTRACT: Novel BN mesoporous nanowire materials with doped oxygen atoms have been controlled and prepared successfully. Multiple techniques have been employed to determine the structure, morphology, surface feature, defects, and electronic structure. It was the first time that a controlled preparation of this unique structure was applied to adsorptive desulfurization. The obtained BN mesoporous nanowires displayed outstanding adsorptive desulfurization activity for DBT (65.4 mg S g−1 adsorbent according to the Langmuir isotherm model), which was much higher than that of commercial BN and graphene-like BN. At the same time, the BN mesoporous nanowires displayed good stability and excellent adsorption performance for the 4,6-DMDBT (33.2 mg S g−1 adsorbent). The significant enhancement of adsorption desulfurization performance of BN mesoporous nanowires was ascribed to the large number of low coordinated atoms along the nanowire surface and mesopores, which could cause an interaction with DBT, and the doped oxygen atoms further strengthen the interaction. KEYWORDS: Boron nitride, Adsorptive desulfurization, Mesoporous nanowires, Oxygen doping

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INTRODUCTION With the increasingly stringent regulations and fuel specifications of the petroleum refining industry, the removal of sulfur compounds from fuels has brought about substantial research interest.1−4 Among different desulfurization processes, adsorptive desulfurization (ADS) has been of particular concern owing to low-energy consumption.5−7 Up to now, different adsorbents have been control-prepared in order to acquire high adsorption desulfurization performance, such as activated carbon,8,9 Cu (or Ag)(I)-containing adsorbents,10−12 metal− organic frameworks (MOFs),13,14 mesoporous silicon,15,16 and so on. Besides, hexagonal boron nitride (h-BN) has been shown promising for adsorptive desulfurization. As the isostructural to graphite, h-BN has aroused increased attention in recent years due to the outstanding physical and chemical properties.17,18 h-BN is a layered structure comprising alternating boron and nitrogen atoms in a honeycomb arrangement, while the boron atoms are sp2 hybridized with electron-deficient virtual orbitals.19 h-BN is in the spotlight for applications as a filler for composites, in graphene-BN hybrid devices, a substrate for graphene electronics, and a support for catalysts.20 Very recently, h-BN was first employed as an adsorbent in adsorptive desulfurization by our group.21 The adsorption capacities were among the highest adsorption capacities reported up to now, which could reach 28.17 mg S g−1 adsorbency according to the Langmuir isotherm model and 20.12 mg S g−1 adsorbency for the 500 ppm sulfur model oil for the removal of dibenzothiophene (DBT). However, it was still © XXXX American Chemical Society

far from enough for potential industrial applications, and it was necessary to tune the structure of BN to further increase the adsorption capacities to meet the potential applications. Generally, the adsorptive processes usually occur on the “‘adsorption sites”’ of materials, in which the low coordinated steps, edges, terraces, kinks, and/or corner atoms are often the favorable activation sites.22,23 Viewed from the point of morphology regulation, building the 1 D nanowires may provide numerous edge sites of BN owing to the layered nature of h-BN. These low coordinated atoms along the surface of 1 D nanowires may be chemically more reactive and could interact with DBT.24 At the same time, the mesoporous can be built on the BN nanowires to increase the amount of low coordinated atoms along the pores.25 Viewed from the point of electronic structure regulation, the chemical doping or defects construction has been employed to tune the electronic structure of materials in many fields, and increased properties have been obtained.26−30 Therefore, doping with a heteroatom in BN may further enhance the adsorptive property. It has been demonstrated in our previous report by density functional theory that the main interaction between BN and DBT came from the occupied π-electrons of DBT and the virtual orbitals of the B atoms.21 Thus, doping the element with large electronegativity such as O to connect with the B atoms could Received: May 28, 2016

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DOI: 10.1021/acssuschemeng.6b01156 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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ACS Sustainable Chemistry & Engineering

Figure 1. (a,b) SEM images and (c,d) TEM images of the BN mesoporous nanowires materials. using KBr disks at room temperature conditions. Electron paramagnetic resonance (EPR) spectra were obtained using a Bruker ESR JES-FA200 spectrometer at 77 K. UV−vis diffuse reflectance spectra (DRS) of the samples were collected using a Shimadzu UV-2450 UV− vis spectrophotometer. Adsorption Experiments. The model oil with different initial sulfur concentrations (100, 200, 300, 500, and 800 ppm) used for adsorption experiments was prepared by dissolving appropriate amounts of DBT in n-octane. In a typical adsorptive desulfurization process, 0.05 g of adsorbent and 20 mL of model oil were added to a 50 mL conical flask, which was placed in a shaker apparatus. Gas chromatography−flame ionization detection (GC-FID) was used for detecting the remaining sulfur concentration in model oil with tetradecane (99%, Sinopharm Chemical Reagent) as the internal standard. The adsorption capacity (qt) of the sulfur compounds was given as

improve the electron-attracting ability, and then, the adsorptive performance may be further increased. Herein, BN mesoporous nanowires with doped O atoms were control-prepared for the first time. Multiple characterizations have been employed to determine the structure, morphology, surface feature, defects, and electronic structure. The obtained BN mesoporous nanowires displayed outstanding adsorption desulfurization performance for DBT (65.4 mg S g−1 adsorbent according to the Langmuir isotherm model; 32.2 mg S g−1 adsorbent for the 500 ppm sulfur model oil), which was much higher than that of commercial BN and graphenelike BN. The relationship between the structure and the adsorptive performance of the BN mesoporous nanowires was also discussed in detail.

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EXPERIMENTAL SECTION

qt =

Materials. All of the reagents used in this research were analytically pure and used without further purification. Boric acid, melamine, naphthalene, and n-octane were purchased from Sinopharm Chemical Reagent. Pluronic P123, dibenzothiophene (DBT), and 4,6dimethyldibenzothiophene (4,6-DMDBT) were purchased from Sigma-Aldrich. n-Hexadecane was obtained from Aladdin Chemistry. Synthesis of BN Mesoporous Nanowires. P123 (0.5 g) was dissolved into the mixture of H2O and methanol (volume ratio 1:2) at 50 °C. Then, boric acid and melamine with a molar ratio of 1:8 were added to the above solution. After the mixture liquid was evaporated completely, the obtained powder was calcined at 1000 °C for 3 h in a nitrogen atmosphere with a heating rate of 5 °C/min. Characterization of the Materials. The scanning electron microscopy (SEM) measurements were carried out with a scanning electron microscope (S4800). Transmission electron microscopy (TEM) images were obtained from a JEOL JEM-2100 transmission electron microscope at an accelerating voltage of 200 kV. Surface areas of the obtained materials were analyzed using the Brunauer−Emmett− Teller (BET) method according to the N2 adsorption−desorption isotherms collected on a TriStar II 3020 surface area and porosity analyzer (Micromeritics Instrument Corporation). The chemical states of the prepared samples were determined via X-ray photoelectron spectroscopy (XPS) using a VG MultiLab 2000 system with a monochromatic Mg−Kα source operated at 20 kV. X-ray diffraction (XRD) of the obtained materials was measured on a Shimadzu XRD6000 X-ray diffractometer using Cu Kα radiation. FTIR spectroscopy was conducted on a Nicolet FTIR spectrophotometer (Nexus 470) by

(C0 − Ct )V m

(1)

where C0 and Ct (mg/L) are the sulfur concentration at times = 0 and t, respectively, V (L) is the volume of the oil, and m (g) is the weight of adsorbent. The experimental data were analyzed by the adsorption isotherms. The linear form of the Langmuir model is Ce C 1 = e + qe qm qmKL

(2)

where qm and qe (mg/g) mean the theoretical maximum adsorption capacity and adsorption capacity of sulfur at equilibrium, respectively, Ce (mg/L) represents the equilibrium concentration of sulfur, and KL (L/mg) is the Langmuir isotherm constant.

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RESULTS AND DISCUSSION The morphology of the as-prepared BN materials was visualized by a scanning electron microscope (SEM). As shown in Figure 1a,b, numerous nanowire structures with the average length of about 1 μm can be seen. The surface microstructure of the obtained BN materials was further investigated by TEM. It can be seen that a large number of mesopores can be found on the surface of BN (Figure 1c,d). These pores would favor the improvement of surface area and expose more interior atoms to the surface. The abundant low B


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190.6 and 398.1 eV were ascribed to B 1s and N 1s, respectively, suggesting that B and N elements existed in the BN mesoporous nanowire sample (Figure 3b,c). The shoulder peak at 192.5 eV in the B 1s spectrum was attributed to the B− O bonds, suggesting that the O atoms have been doped into the BN successfully. The electronegativity of the oxygen atom was much larger than the boron atom. In B 1s high-resolution XPS spectra (Figure 3b), the peak at 192.5 eV was at a higher binding energy than that for pure h-BN (190.6 eV). This indicated that some of the boron atoms in the BN mesopore nanowires are more electropositive than that in pure h-BN. The chemical shift can be explained by a boron adjacent to oxygen atoms, where oxygen atoms could partly attract the electron of the coterminal boron atoms. The similar results can also be found in the literature.32,33 Figure 3d shows the high-resolution XPS spectra of O 1s, which further revealed that the O element has been introduced to the BN materials. The structure of the sample was investigated by XRD and FTIR spectroscopy. As shown in Figure 4a, the as-prepared BN material displayed two broad peaks around 24° and 43°, corresponding to the (002) and (100) crystal facet, suggesting the poor crystallization of the obtained BN material.34 This was consistent with the TEM analysis that numerous pores on the BN decreased the crystallization. Compared with the graphenelike BN, the (002) diffraction peaks of BN mesoporous nanowires shifted slightly to lower angles. This feature could be interpreted as the introduction of oxygen heteroatoms and the disturbance of the h-BN structure.35 More details of the structure were acquired from the FTIR analysis, and the results are shown in Figure 4b. Two strong characteristic bands at about 1390 and 800 cm−1 can be seen for both the BN mesoporous nanowires and graphene-like BN materials, corresponding to the in-plane B−N stretching vibrations and out-of-plane B−N−B bending vibrations, respectively.36,37 Compared with the graphene-like BN, a new peak at 1045 cm−1 appeared in the BN mesoporous nanowires sample. The peak was derived from the B−O vibration, revealing that the O atom has been incorporated in the BN mesoporous nanowires.38,39 This was in good agreement with the XPS and XRD analyses. Since the defects may be generated along the pores during the synthetic process, the EPR spectrum was employed to determine the existence of defects in the prepared BN mesoporous nanowires. As shown in the Figure 4c, no signal attributable to the defects can be observed, suggesting that the defect was not the main factor to affect the adsorption performance of the obtained BN mesoporous nanowires. The O element may be incorporated along the pores, and the singleelectron-trapped defects were not generated.40 UV−vis DRS was employed to characterize the absorption property of the BN mesoporous nanowires and graphene-like BN materials, and the results are displayed in Figure 4d. The graphene-like BN has an absorption onset at 310 nm, which corresponds to a band gap of 4 eV as determined by the Kubelka−Munk theory. With respect to the BN mesoporous nanowires, the absorption extended to the visible light region accompanied by shoulder and tail peaks.41 Generally, this improved absorption was derived from the defect state or the dopant states. In this system, the doped O atom accounted for the improved absorption owing to the fact the defects did not exist in the BN mesoporous nanowires. To explore the usefulness of the as-prepared BN mesoporous nanowires, adsorption and removal DBT of the model oil was

coordinated atoms along the surface of nanowires and the edges of the pores were chemically more reactive and may act as strong adsorption sites.22 At the same time, the presence of numerous pores facilitated easy model oil infiltration into the interior BN mesoporous nanowires and hence ensured good contact with DBT, thus greatly improving their adsorptive process.24 The above results indicate that the BN nanowires with surface mesopores can be control-prepared. The nitrogen adsorption and desorption isotherms were performed to study the BET specific surface area and pore size distributions. As shown in Figure 2a, the adsorption−

Figure 2. (a) N2 adsorption−desorption isotherms and (b) the BJH pore-size distribution curves of BN mesoporous nanowires.

desorption isotherm of the obtained BN materials displayed typical IV-type curves with an H1-type hysteresis loop, indicating the presence of a mesopore (2−50 nm) on the BN sample. The obtained BN sample displayed a BET surface area of 295 m2 g−1, much larger than the BET surface area of graphene-like BN materials (167 m2 g−1) in our previous report.21 It has been widely recognized that a higher BET surface area would provide more adsorption sites and then enable increased adsorptive performance.31 As shown in Figure 2b, the pore size distribution was obtained using the Barrett− Joyner−Halenda model with the peak centered at 2.5 nm, and the pore volume was 0.37 cm3/g. This result was in good agreement with the TEM analysis, suggesting that the numerous mesopores existed on the BN nanowires. XPS was employed to investigate the surface elements and chemical states of BN mesoporous nanowires materials. Figure 3a was the survey scan XPS spectrum, which clearly indicated that the BN mesoporous nanowire sample was mainly composed of B, N, O, and C elements. The carbon peak came from the adventitious carbon. The binding energies at C


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Figure 3. XPS spectra of the BN mesoporous nanowires. (a) Survey of the sample; (b) B 1s; (c) N 1s; and (d) O 1s.

Figure 4. (a) XRD, (b) FTIR, (c) EPR, and (d) DRS analysis of the BN mesoporous nanowires.

mesoporous nanowires for DBT was also much higher than the values reported in other papers.42−47 It has been demonstrated in our previous report by density functional theory that the main interaction between BN and DBT came from the occupied π-electrons of DBT and the virtual orbitals of the boron atoms.21 In this system, the large number of low coordinated atoms along the mesopore could cause an interaction with DBT, and the high electronegativity O atoms would attract the electron cloud of the coterminal B atoms and

tested (Figure 5). After adsorption for 180 min, the adsorption capacity of 1.2 mg S g−1 adsorbent was acquired by the commercial BN, and graphene-like BN was also employed to make a comparison, which could display the adsorption capacity of 20.12 mg S g−1 adsorbent.21 With respect to the BN mesoporous nanowires, the adsorption capacity could reach 32.2 mg S g−1 adsorbent within the same time, which was 16.8 and 1.6 times higher than that of the commercial BN and graphene-like BN, respectively. This adsorption capacity of BN D


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been completely removed. As a result, the adsorption capacity is somewhat decreased. In order to investigate the temperature−adsorption capacity relationship, in this system, different temperatures of 298, 303, 313, 333, and 353 K were tested by using BN mesoporous nanowires samples and 500 ppm of S DBT model oil. As shown in Figure 7, when the temperature increased, the adsorption

Figure 5. Adsorption capacities of different BN samples. Experimental conditions: 500 ppm initial sulfur concentration, V (oil) = 20 mL, m (adsorbent) = 0.05 g, T = 298 K, and atmospheric pressure.

increase the electropositivity of virtual orbitals in B atoms. As a result, the BN mesoporous nanowires could construct powerful interactions with DBT, and an excellent adsorption desulfurization performance was obtained. The reusability and stability of the adsorbents are vital to practical applications. To evaluate the reusability and stability of the BN mesoporous nanowire material, recycling reactions are performed for the adsorption of DBT (Figure 6). After five consecutive cycles, the adsorption

Figure 7. Effect of temperature on DBT adsorption by BN mesoporous nanowires. Experimental conditions: 500 ppm initial sulfur concentration, V (oil) = 20 mL, m (adsorbent) = 0.05 g, and atmospheric pressure.

capacity of DBT gradually decreased. As the temperature increased from 298 to 353 K, the DBT adsorption capacity decreased from 32.2 to 23 mg S g−1 adsorbent, revealing the exothermic process during the DBT adsorption. Therefore, room temperature was beneficial to adsorptive desulfurization by BN mesoporous nanowires. To assess the effect of DBT initial concentration on adsorption capacity, different DBT initial concentrations were also studied with BN mesoporous nanowire samples as adsorbent at 298 K. As shown in Figure 8, with the

Figure 6. Recycle times of the DBT removal with BN mesoporous nanowires as adsorbent. Experimental conditions: 500 ppm initial sulfur concentration, V (oil) = 20 mL, m (adsorbent) = 0.05 g, T = 298 K, and atmospheric pressure.

capacity can still be maintained (27.1 mg S g−1 adsorbent), which implies the high stability of BN mesoporous nanowire material. It can be seen that the adsorption capacity of the used BN sample is a little reduced, which can be attributed to the fact that the DBT adsorbed on the BN surface has not been completely removed. Because the used BN mesopore nanowire material was regenerated by toluene washing several times at 80 °C, the washing process is in competition and causes a dynamic balance process between the BN−DBT interaction and the toluene−DBT interaction. The specific surface area of the spent BN material was analyzed by N2 adsorption−desorption measurements. The BET specific surface area of spent BN mesopore nanowires material was calculated to be 171 m2 g−1, which is smaller than that of the fresh BN mesopore nanowires (295 m2 g−1). The decrease of specific surface area can be attributed to the DBT adsorbed on the BN surface that has not

Figure 8. Effect of initial sulfur concentration on DBT adsorption by BN mesoporous nanowires. Experimental conditions: V (oil) = 20 mL, m (adsorbent) = 0.05 g, T = 298 K, and atmospheric pressure.

improvement of DBT initial concentration, the adsorption capacity of BN mesoporous nanowires gradually increased. The BN mesoporous nanowires displayed the balanced adsorption capacity of 12.2, 18.3, 24, 32.2, and 44.3 mg S g−1 adsorbent for the model oil of 100, 200, 300, 500, and 800 ppm initial sulfur concentration, respectively. This result was attributed to the fact that the initial concentration provided an important driving force to overcome mass transfer resistance of solutes between E


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ACS Sustainable Chemistry & Engineering the oil and solid phases.21 The Langmuir isotherm model was used to evaluate the maximum adsorption capacity of DBT on the obtained BN mesoporous nanowires, as displayed in Figure 9. The adsorption equilibrium concentration vs adsorption

As we know, the components of real fuel are complex. In order to represent desulfurization of real fuel, a model fuel containing 10 wt % naphthalene was prepared with different initial sulfur concentrations (500 ppm of S for DBT and 350 ppm of S for 4,6-DMDBT) by dissolving appropriate amounts of DBT and 4,6-DMDBT in paraffinic solvent n-hexadecane. Figure 11 presents the adsorption capacity with BN

Figure 9. Langmuir isotherm of DBT adsorbed on BN mesoporous nanowires. Figure 11. Effect of aromatic compound on adsorption capacity. Experimental conditions: n-hexadecane as solvent, V (oil) = 20 mL, m (adsorbent) = 0.05 g, T = 298 K, and atmospheric pressure.

capacity well fitted the Langmuir isotherm model, with a correlation coefficient of 0.9503. The maximum adsorption capacity of DBT on BN mesoporous nanowires was 65.4 mg S g−1 adsorbent. To the best of our knowledge, this adsorption capacity was one of the highest values reported up to now and is much higher than our previous reports.21,34,48 4,6-DMDBT was also employed to further evaluate the adsorption performance of the obtained BN mesoporous nanowires at 298 K. As is well-known, owing to its aromaticity and steric hindrance of the two methyl, 4,6-DMDBT was difficult to removed through hydrodesulfurization, oxidative desulfurization, or extractive desulfurization.49,50 Hence, it is greatly important to remove 4,6-DMDBT. As shown in Figure 10, the BN mesoporous nanowires could also display excellent

mesoporous nanowires as the adsorbent. It can be seen that when n-octane was replaced with paraffin n-hexadecane as the solvent, without naphthalene added, the adsorption capacity was 33.8 and 25.2 mg S g−1 adsorbent for DBT and 4,6DMDBT, respectively. With naphthalene added, the adsorption capacity showed a slight decrease, and BN mesopore nanowires still revealed high adsorption performance with a DBT adsorption capacity of 28 mg S g−1 adsorbent and a 4,6DMDBT adsorption capacity of 22 mg S g−1 adsorbent. The other adsorbents reported in the literature with the aromatic compounds in liquid fuels were used for comparative evaluation. For 687 and 303 ppm of total sulfur concentration and nitrogen concentration in the fuel containing 10 wt % of butybenzene, the capacity of 2.18 mg S g−1 adsorbent was reported for Ni/SiO2−Al2O3.52 On the Ce-Exchanged Y Zeolites, the adsorption capacity measured using Model Jet Fuel with a total sulfur content of about 510 ppmw and 3.9 mmol/L naphthalene and 1-methylnaphthalene was 13.8 mg S g−1adsorbent.53 Using 300 ppmw S in fuel with 15% toluene reported DBT and DMDBT capacities on MOF-505 to be 14 and 9 mg S g−1adsorbent, respectively.43 Adsorption of DBT and 4,6-DMDBT from simulated diesel fuel with 20 ppmw total concentration of sulfur and containing 2.35 × 10−7 mol/mL naphthalene and 1-methylnaphthalene, was 9.94 mg S g−1adsorbent for the total adsorption capacity of polymerderived carbon.54 As a result, the BN mesoporous nanowires with doped O atoms obtained in this system may be an ideal adsorbent for sulfur removal.

Figure 10. Adsorption capacities of BN mesoporous nanowires on 4,6DMDBT. Experimental conditions: 400 ppm initial sulfur concentration, V (oil) = 20 mL, m (adsorbent) = 0.05 g, T = 298 K, andatmospheric pressure.

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CONCLUSIONS Novel BN mesoporous nanowire materials with doped O atoms have been control-prepared successfully. The obtained BN mesoporous nanowires displayed outstanding adsorption desulfurization performance for DBT (65.4 mg S g−1 adsorbent according to the Langmuir isotherm model) and 4,6-DMDBT (33.2 mg S/g adsorbent). The adsorption capacity of BN mesoporous nanowires was one of the highest values reported up to now. In addition, the BN mesoporous nanowires displayed excellent reusability and stability, which was valuable

adsorption performance for 4,6-DMDBT (400 ppm initial sulfur concentration), and the adsorption capacity could reach 33.2 mg S g−1 adsorbent. The adsorption capacity for 4,6DMDBT in this system was much higher than those in the literature.43,47,51 Considering the low-cost, robust, nontoxic, metal-free nature, and high adsorption capacity, the BN mesoporous nanowire material display the possibility to meet the requirements of potential industrial applications. F


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for the potential applications for adsorption desulfurization. Compared to the commercial BN and graphene-like BN materials, the significant enhancement of adsorption desulfurization performance of BN mesoporous nanowires was ascribed to the large number of low coordinated atoms along the nanowire surface and mesopores, which could cause an interaction with DBT, and the doped O atoms further strengthen the interaction.

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AUTHOR INFORMATION

Corresponding Authors

*(W.S.Z.) E-mail: [email protected]. *(H.M.L.) E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank the National Natural Science Foundation of China (nos. 21376111, 21576122, and 21506083), Six Big Talent Peak in Jiangsu province (JNHB-004), the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), and the Postdoctoral Foundation of China (no. 2015M580399) for financial support.

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REFERENCES

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Boron Nitride Mesoporous Nanowires with Doped Oxygen Atoms for

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