This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
Article Cite This: ACS Omega 2018, 3, 1350−1356
Influence of Molecular Weight on Structure and Catalytic Characteristics of Ordered Mesoporous Carbon Derived from Lignin Hengfei Qin,† Ruihong Jian,‡ Jirong Bai,§ Jianghong Tang,† Yue Zhou,† Binglong Zhu,† Dejian Zhao,† Zhijiang Ni,§ Liangbiao Wang,† Weiqiao Liu,† Quanfa Zhou,*,† and Xi Li*,§ †
Jiangsu Key Laboratory of E-Waste Recycling, Department of Chemistry and Environmental Engineering, Jiangsu University of Technology, Changzhou 213001, China ‡ Department of Industrial Catalysis, Petro China Fushun Petrochemical Company Catalyst Plant, Fushun 113008, China § Department of Environmental Science and Engineering, Fudan University, Shanghai 200433, China S Supporting Information *
ABSTRACT: Bio-renewable lignin has been used as a carbon source for the preparation of porous carbon materials. Nevertheless, up to now, there are few studies about the influence of molecular weight of lignin on the structure and morphology of the ordered mesoporous carbon. Here, we synthesized the ordered mesoporous carbon derived from different molecular weights of lignin and Pluronic F127. Fortunately, we found that molecular weight is an important factor for obtaining highly ordered channels, high specific surface area, and ordered mesoporous carbon. More importantly, the narrow well-defined mesoporous channel could exert a spatial restriction effect to some extent, which can serve as nanoreactors for efficient reactions and enhance catalytic performance. The highly ordered mesoporous carbon from lignin is a good candidate for Fischer−Tropsch synthesis catalyst supports.
■
INTRODUCTION Over the past decades, carbon materials have received significant interest because of their unique geometrical structure and chemical properties. These materials have been used in a broad range of applications, such as electrode materials,1 fuel cells,2 adsorbents,3 supercapacitors,4,5 and catalyst supports.6 Among these carbon materials, activated carbon, carbon nanotubes, and graphene have been studied widely as catalyst supports. Besides these carbon materials, the ordered mesoporous carbon has received increasing attention because of their chemical inertness, good thermal stability, excellent catalytic activity, high surface area, and easily tunable pore sizes.7 Currently, the ordered mesoporous carbon was successively fabricated by a hard-template method8 or a softtemplate method.9 Although great progress has been made in the preparation of the ordered mesoporous carbon, there are some details that remain to be investigated. First, the carbon sources are related to toxic substances, such as phenol, 3aminophenol, phloroglucinol, and hexaphenol,10−13 which are unsustainable substances. Furthermore, there are few studies on the influence of molecular weight of the carbon source on the pore structure and specific surface area. Therefore, seeking © 2018 American Chemical Society
sustainable carbon sources and the study of the molecular weight of carbon sources are significant to the physical and chemical properties of the ordered mesoporous carbon. Lignin is a low-cost, nontoxic, and carbon-rich sustainable resource, which is the second most abundant amorphous polymer in nature.14,15 It can be obtained from a variety of sources, such as woody plants, byproducts in paper factories, and even from industrial waste of biomass ethanol.16,17 Lignin is a highly branched aromatic polymer consisting of the phenylpropane coniferyl, p-coumaryl, and sinapyl alcohol as monomer units with a large amount of functionalities, such as methoxy, carbonyl, and hydroxyl groups.17−19 Considering the structural similarity of lignin with phenol (−OH), lignin can be a promising natural alternative for phenolic resins in the synthesis of the ordered mesoporous carbon. More importantly, lignin is a nontoxic, low-cost, bio-renewable, and sustainable carbon source. Received: November 28, 2017 Accepted: January 19, 2018 Published: January 31, 2018 1350
DOI: 10.1021/acsomega.7b01870 ACS Omega 2018, 3, 1350−1356
Article
ACS Omega Table 1. Physicochemical Properties of CESL-5, CSL-5, and CSL-2
a
sample
surface areaa (m2·g−1)
ESL-5 SL-5 SL-2 CESL-5 CSL-5 CSL-2
12.3 9.8 11.7 236.4 435.0 466.1
pore sizea (nm)
pore volumea (cm3·g−1)
Mwb (g·mol−1) 2996 1476 1055
3.8 3.8 3.8
0.48 0.57 0.62
Determined by N2 physisorption. bThe molecular weight was determined by GPC.
Figure 1. (a) Low-angle XRD patterns and (b) N2 adsorption−desorption isotherms of the ordered mesoporous carbon with different molecular weights of lignin.
respectively. From the N2 adsorption−desorption isotherm results, the Brunauer−Emmett−Teller (BET) surface areas of the lignin precursors (ESL-5, SL-5, and SL-2) were 12.3, 9.8, 11.7 m2·g−1, respectively. The low-angle X-ray diffraction (XRD) patterns of CSL-2, CSL-5, and CESL-5 are shown in Figure 1a. All of the sample exhibits an intense diffraction peak at around 0.98 and a weak peak at around 1.4, which can be indexed as (100) and (110) reflections associated with hexagonal pore regularity of a p6mm space group.12,25 Meanwhile, with the increase of molecular weight, the diffraction peak intensities of (100) and (110) crystal planes decrease significantly, the 100 diffraction peak becomes less visible in CSL-5 and CESL-5, and the 110 diffraction peak even disappears in CESL-5. However, all of the diffraction peaks of CSL-2 are obviously visible, which suggests that the molecular weight of the precursor is a key factor for the formation of the ordered mesoporous carbon. The N2 adsorption−desorption isotherms of the ordered mesoporous carbon synthesized using different molecular weights are shown in Figure 1b. The CSL-2, CSL-5, and CESL-5 exhibit a type IV isotherm with a H1-type hysteresis loop and large uptake at a low relative pressure, indicating mesoporous and microporous characteristics.26 Moreover, the hysteresis loop of the H1-type hysteresis loop in the relative pressure at P/P0 = 0.45−0.75 reflects a high uniformity of mesoporous structures.27 The mesoporous structure is derived from the removal of the surfactant F127. In addition, a high increase of nitrogen uptake at a low relative pressure (P/P0 = 0.01−0.1) corresponds to the volume adsorbed by micropores, which may originate from the lignin framework during the pyrolysis process of C, H, and O combustion.9,28 The pore size distributions were calculated from the branches of the adsorption isotherms using the Barrett−Joyner−Halenda (BJH) model, and all the samples show similar shapes with uniform mesopores, and most pore diameters of obtained samples are all centered at about 3.8 nm (Figure 1 inset). In
Actually, there have been tremendous efforts to obtain carbon materials from lignin because of the abovementioned advantages. There are numerous reports on the preparation of the porous carbon from lignin.20 In general, most studies focus on the effect of templating agents on the pore structure or activating agents on the specific surface area. Commonly, zeolites and Pluronic F1278 are used as the templating agents, KOH21 and CO2 are used as the activating agents. Under these circumstances, the pore structure and surface area were strongly dependent on the type of the template and activating agent. However, lignin has no structural regularity in the polymeric framework, with a wide molecular weight distribution, generally ranging from several thousand to hundreds of thousands. Therefore, the preparation of the ordered mesoporous carbon with lignin as the carbon source is critical for its molecular weight. Owing to this reason, we are motivated to discuss the formation of the ordered mesoporous carbon from lignin with different molecular weights. Herein, we report for the first time the synthesis of the ordered mesoporous carbon by the soft-template method using lignin as the carbon source with different molecular weights. The focus of the work is to investigate the effects of the lignin molecular weight on the morphology and structure of the ordered mesoporous carbon. Then, we study the catalytic performance of the ordered mesoporous carbon as the catalyst support of Fischer−Tropsch synthesis (FTS). In addition, from a practical point of view, the ordered mesoporous carbon for FTS applications is desirable for industrial mass production because of the sustainable carbon sources of lignin.
■
RESULTS AND DISCUSSION The textural parameters of ESL-5, SL-5, and SL-2 obtained from different extraction methods of lignin are listed in Table 1. The average molecular weight (Mw) was determined by gel permeation chromatography (GPC). The Mw values of ESL-5, SL-5, and SL-2 were 2996, 1476, and 1055 g·mol−1, 1351
DOI: 10.1021/acsomega.7b01870 ACS Omega 2018, 3, 1350−1356
Article
ACS Omega
Figure 2. TEM images of the ordered mesoporous carbon with different molecular weights of lignin: (a,b) CSL-2; (c,d) CSL-5; and (e,f) CESL-5.
Figure 3. (a) XRD patterns and (b) Fe 2p spectra of Fe/CSL-2, Fe/CSL-5, and Fe/CESL-5.
addition, the N2 adsorption−desorption isotherms (Figure 1b) exhibit a strong uptake at a low pressure of approximately 0.01−0.04, suggesting microporous characteristics. As can be seen from Table 1, the surface area and the pore volume of the ordered mesoporous carbon obtained from low-molecularweight lignin are higher than those of high-molecular-weight lignin. The specific surface area and the pore volume have reached to 466.1 m2·g−1 and 0.62 cm3·g−1, respectively, which reveals that CSL-2 reaches well-order at long-range distances. With further increase in the molecular weight from 1476 to 2966 g·mol−1, the surface area and pore volumes of CSL-5 and CESL-5 decrease from 435.0 m2·g−1 and 0.58 cm3·g−1 to 236.4 m2·g−1 and 0.47 cm3·g−1, respectively, demonstrating that with the increase of molecular weights, the order of the mesoporous structure was disrupted. CSL-2 and CSL-5 show a higher surface area and pore volume than CESL-5, which indicates that the molecular weight of the precursor is a critical parameter to obtain the ordered mesoporous carbon.
Transmission electron microscopy (TEM) was used to inspect the morphology and microstructure of CSL-2, CSL-5, and CESL-5. As shown in Figure 2, all the samples display a mesoporous structure. The CSL-2 with the molecular weight of 1055 g·mol−1 (Figure 2a,b) exhibits hexagonally arranged and stripe-like patterns in large domains, authenticating an ordered 2D hexagonal mesoporous characteristics. When the molecular weight increases to 1476 g·mol−1, CSL-5 shows results similar to CSL-2 from the TEM observation (Figure 2c,d), further confirming the successful formation of an ordered mesostructure. However, when the molecular weight reaches 2996 g· mol−1, the mesoporous ordering of CESL-5 (Figure 2e,f) is much weaker than that of CSL-2, which agrees with the results of low-angle XRD. On the basis of the abovementioned analysis, the lignin with a small molecular weight is beneficial to the formation of the long-range ordered mesoporous carbon, and the channel is straight. With the increase of the molecular weight, the pore ordering becomes worse, short range, and even chaotic. This phenomenon could be explained by the facts that 1352
DOI: 10.1021/acsomega.7b01870 ACS Omega 2018, 3, 1350−1356
Article
ACS Omega
Figure 4. TEM images of Fe/CSL-2 (a,b), Fe/CSL-5 (c,d), and Fe/CESL-5 (e,f).
Fe3+ state,31 which is in accord with the results of XRD pattern results. TEM images of Fe/CSL-2, Fe/CSL-5, and Fe/CESL-5 nanocomposites show stripe-like patterns in large domains, confirming ordered mesoporous characteristics (Figure 4). The dark spots are observed for iron nanoparticles, which are dispersed homogeneously in the matrix of the ordered mesoporous carbon. From the TEM images of Fe/CSL-2 and Fe/CSL-5 (Figure 4a−d), we can see that the Fe2O3 particles were dispersed homogeneously in the carbon matrix without aggregation, and most of the Fe2O3 nanoparticle distribution curve demonstrates a mean diameter of about 9−10 nm (Figure 4a,c, inset). However, slight agglomeration began to occur in Fe/CESL-5 (Figure 4e,f), and the size of Fe2O3 nanoparticles in Fe/CESL-5 is approximately 12 nm (Figure 4e, inset). Fe/CSL-2, Fe/CSL-5, and Fe/CESL-5 were studied as catalysts in FTS reaction. Table 2 and Figure 5 summarize the hydrocarbon product distribution, lower olefin selectivity, and
(i) low-molecular-weight lignin has more hydroxyl groups in unit mass, conducive formation of micelles with the block copolymer surfactants (F127), which is easy to form the ordered mesoporous structure28 and (ii) low-molecular-weight lignin perhaps has higher chain mobility, making lignin segments easier to carbonize, resulting in a more ordered mesoporous structure. On the basis of the abovementioned analysis, it can be conjectured that large-molecular-weight precursors are unfavorable to the formation of the ordered mesoporous carbon.29 Therefore, to obtain carbon materials with a highly ordered pore structure and a large specific surface area, a relatively low-molecular-weight precursor should be considered. XRD was performed to identify the crystal phase of Fe/CSL2, Fe/CSL-5, and Fe/CESL-5. It can be seen from Figure 3a that the five broad peaks at around 30.2°, 35.6°, 43.3°, 57.2°, and 62.9° are indexed to the (220), (311), (400), (511), and (440) reflection for magnetite, respectively (Fe3O4, JCPDS card no. 39-1346). The X-ray photoelectron spectroscopy (XPS) analysis was further employed to analyze the surface composition of Fe/CSL-2, Fe/CSL-5, and Fe/CESL-5. The data of XPS spectrum analysis are presented in Figures 3b and S1 (Supporting Information). Three main peaks of C 1s, O 1s, and Fe 2p were present in all spectra (Figure S1, Supporting Information) because Fe/CSL-2, Fe/CSL-5, and Fe/CESL-5 contain only C, O, and Fe elements.30 The Fe 2p binding energy spectra of Fe/CSL-2, Fe/CSL-5, and Fe/CESL-5 are shown in Figure 3b. The peaks at around 710.9 and 724.2 eV are assigned to Fe 2p3/2 and Fe 2p1/2 peaks, respectively. The 718.8 eV binding energy was attributed to the satellite peak of Fe 2p3/2. The satellite peak and the 13.3 eV difference between Fe 2p3/2 and Fe 2p1/2 peaks indicate the characteristics of the
Table 2. FTS Catalytic Performance of Fe/CSL-2, Fe/CSL-5, and Fe/CESL-5 selectivityb (%)
catalyst
CO conv. (%)
CH4
C2−C4 olefins
C2−C4 paraffines
C5+
O/Pc
Fe/CSL-2a Fe/CSL-5a Fe/CESL-5a
86.1 82.3 69.4
25.3 24.6 28.9
43.1 41.3 35.4
11.4 13.6 16.4
20.2 20.5 19.3
3.78 3.04 2.16
Reaction condition: T = 350 °C, P = 2 MPa, H2/CO = 1, GHSV = 4.5 L/h/gcat, TOS = 36 h. bHydrocarbon selectivity was normalized with the exception of CO2. cO/P is the ratio of olefin to paraffin in all of the C2−4 hydrocarbons. a
1353
DOI: 10.1021/acsomega.7b01870 ACS Omega 2018, 3, 1350−1356
Article
ACS Omega
Figure 5. Catalytic performances in FTS: (a) plots of C2-C4 olefins, paraffines, and CH4 selectivity and (b) conversions of CO with time on stream for Fe/CSL-2, Fe/CSL-5, and Fe/CESL-5.
higher surface area and well-defined mesoporous channels than CESL-5, which suggested that the molecular weight of lignin plays an important role in the preparation of the ordered mesoporous carbon. Furthermore, because of their unique pore structure, smaller iron nanoparticles, and spatial confinement effect, Fe/CSL-2 and Fe/CSL-5 exhibit higher O/P (3.78 and 3.04) in the FTO reaction. Utilizing lignin-based porous materials with a controlled pore channel structure in energyrelated applications will promote the development of paper mills and biomass ethanol refineries and enhance sustainability.
other performance of all the catalysts. CO conversion is a rough measure of the FTS reaction of catalysts. As can be seen in Table 2, Fe/CSL-2 and Fe/CSL-5 catalysts exhibit higher CO conversion than Fe/CESL-5 (86.1, 82.3, and 69.4%, respectively). First, according to the results of XRD, Fe/CSL-2 and Fe/CSL-5 exhibit regular ordered mesoporous channels, which are favorable for mass transfer and diffusion. This may be one reason for the higher CO conversion. Second, according to the results of N2 adsorption−desorption isotherms, Fe/CSL-2 and Fe/CSL-5 display a higher surface area, which can provide more adsorption sites and promote the conversion of CO. Furthermore, Fe/CSL-2 and Fe/CSL-5 show Fe2O3 nanoparticles smaller than Fe/CESL-5, which can help to increase CO conversion.9 The product distributions of all catalysts are shown in Table 2 and Figure 5a. CH4 selectivity for Fe/CESL-5 (28.9%) is more than that for Fe/CSL-2 and Fe/CSL-5 (25.3 and 24.6%). However, the C2−C4 olefin selectivity increases from 35.4% (Fe/CESL-5) to 41.3 and 43.1% (for Fe/CSL-5 and Fe/CSL-2, respectively). C=/Cn is an important index of FTS to lower olefins (FTO). It can be also seen in Table 2 that Fe/CSL-2 and Fe/CSL-5 with smaller Fe2O3 nanoparticles and regular ordered mesoporous channels (3.78 and 3.04) exhibit higher O/P than Fe/CESL-5 (2.16). On the basis of the abovementioned analysis, Fe/CSL-2 and Fe/CSL-5 exhibit excellent FTO performance because of the unique regular ordered mesoporous channels, highly dispersed active phases, smaller Fe2O3 nanoparticles, and weaker interactions with supports.32 To further study the catalytic performance, Figure 5b shows the CO conversion of Fe/CSL-2, Fe/CSL-5, and Fe/CESL-5 as a function of time on stream. The CO conversions of Fe/CSL-2 and Fe/CSL-5 catalysts were 86.6 and 82.5% initially and then decreased to 80.1 and 75.9% after 68 h on stream; no significant decrease was observed in the following reaction time. However, the CO conversion of Fe/CESL-5 dropped much faster (from 69.4 to 59.5%) after 68 h on stream. Fe/CSL-2 and Fe/CSL-5 show excellent catalytic performance, which may be attributed to smaller Fe2O3 nanoparticles that were embedded in the ordered mesoporous carbon matrix, effectively avoiding agglomeration and sintering during the FTO reaction.33
■
EXPERIMENTAL SECTION Preparation of Lignin with Different Molecular Weights. Soft wood lignin was purchased from Nanjing Forestry University. The lignin contained a large number of G and S units; the number of G units in lignin is more than S units. The lignin was used as received without further purification. First, lignin was dissolved in water solution under stirring at room temperature which is added to 1 wt % NaOH to adjust the pH = 9−10 and then into 5% HNO3 to adjust the pH = 2 and pH = 5. It was followed by centrifugation at 4200 rpm for 5 min and washing with water until pH = 7. Finally, it is dried at 120 °C for 3 h. The obtained lignin was labeled as SL-2 and SL-5. The straw lignin was extracted from straw feedstock, and ethanol was used as solvent. First, the straw was packed with weighing paper, then placed in a Soxhlet extractor, added to ethanol, installed in a condenser tube, and returned at 100 °C for 6 h, and finally, straw lignin was obtained; it was then added into 5% HNO3 to adjust the pH = 5. It was followed by centrifugation at 4200 rpm for 5 min and washing with water until pH = 7. Finally, it was dried at 120 °C for 3 h. The obtained lignin was labeled as ESL-5. Synthesis of Lignin-Based Oligomer Precursors. The precursors were prepared by using lignin and formaldehyde according to our own method.16,22 Typically, 1.0 g of lignin was added into 12.0 g of 3 wt % NaOH water solution under stirring at 40 °C, and 1.6 g of formalin solution (37 wt % formalin) was subsequently added; then, the temperature was raised to 70 °C, and reaction took place for 1.5 h; after that, it was added into 1% HNO3 to adjust the pH = 5. Finally, the lignin-based oligomer precursors were dissolved in 20 wt % water solution. Preparation of the Ordered Mesoporous Carbon. The ordered mesoporous carbons were synthesized by the softtemplate method. For a typical preparation, 3 g of Pluronic F127 was added into 40 g of precursors. After stirring for 2 h, the brown mixture was dried at 50 °C for 24 h, then the
■
CONCLUSIONS In summary, we successfully synthesized the ordered mesoporous carbon from renewable lignin precursors using the surfactant Pluronic F127 as the pore-forming agent. According to the results of low-angle XRD, N2 adsorption− desorption isotherms, and TEM, CSL-2 and CSL-5 show 1354
DOI: 10.1021/acsomega.7b01870 ACS Omega 2018, 3, 1350−1356
Article
ACS Omega temperature raised to 120 °C for 24 h. Finally, the composites were carbonized at 600 °C for 3 h with a ramping rate of 1 °C/ min under an argon flow. The obtained samples were denoted as CSL-2, CSL-5, and CESL-5. Synthesis of Iron Nanoparticle-Incorporated Mesoporous Carbon Composites. The iron nanoparticleincorporated mesoporous carbon composites were prepared by the impregnating method. For a typical preparation, 1.0 g of ordered mesoporous carbons was dispersed in 60 mL of deionized water by ultrasonication for 2 h to obtain a black suspension, and then 1.0 g of iron nitrate nonahydrate dissolved in 25 mL of ethanol was added to the black suspension with stirring. After the suspension was stirred at room temperature for 8 h, the mixture was heated to 120 °C for 24 h. Finally, the composites were carbonized at 350 °C for 3 h with a ramping rate of 1 °C/min under the argon flow. The obtained samples were denoted as Fe/CSL-2, Fe/CSL-5, and Fe/CESL-5. Measurements and Characterizations. Conventional powder XRD patterns were acquired on a Rigaku D/Max2rBII X-ray diffractometer (XRD, Cu Kα radiation, λ = 1.5406 Å) operated at 40 kV and 100 mA (scanning step 8°/s). The lowangle XRD patterns were collected on a D/max-2500 diffractometer (Cu Kα radiation, 40 kV and 150 mA). GPC analyses were carried out using a UV detector on a 4-column sequence of Waters Styragel columns (HR0.5, HR2, HR4 and HR6) at a 1.00 mL/min flow rate.23,24 TEM images were recorded on a JEOL JEM-2010 electron microscope operated at 200 kV. Nitrogen sorption isotherms were measured at −196 °C on an automated volumetric apparatus NOVA 2000e (Quantachrome Instruments, USA). The multipoint BET method was utilized to calculate the specific surface areas and the pore volume. Pore size distribution was determined from the adsorption branch of the isotherm using the BJH model. The X-ray photoelectron spectrum date was obtained with a PerkinElmer PHI5000C XPS meter with Al Kα radiation (hν = 1486.6 eV) as the excitation source. FTS products were conducted online with two gas chromatographs. The GC9860 gas chromatograph equipped with 2 m long TDX-01 connected to the thermal conductivity detector was used to analyze H2, N2, CO, CH4, and CO2, whereas hydrocarbons (C1−C30) were analyzed by a GC9860 gas chromatograph equipped with a PONA capillary column (50 m × 0.25 mm × 0.50 μm) connected to a flame ionization detector.
■
Author Contributions
X.L., Q.Z., and H.Q. designed the synthetic scheme for the ordered mesoporous carbon. R.J. and H.Q. evaluated the activity of catalyst. H.Q., J.T., Y.Z., B.Z., D.Z., and J.B. obtained the X-ray diffraction and nitrogen sorption isotherms data. J.B. and Z.N. performed the transmission electron microscope imaging, X-ray photoelectron spectrum, and data analysis. X.L and Q.Z. designed the overall project and were involved in the interpretation of data. All authors participated in manuscript written and revision. Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
REFERENCES
The project is financially supported by the National financial supports from National Natural Science Foundation of China (grant no. 2014BAC03B06), Natural Science Foundation of the Higher Educations Institutions of Jiangsu Province (no. 17KJB430014), Talent introduction project of Jiangsu University of Technology (no. KYY16021), and brand specialty of Jiangsu University of Technology. We also acknowledge Lihui Zhou for the assistance in TEM imaging.
(1) Zhang, Y.; Bo, X.; Nsabimana, A.; Munyentwali, A.; Han, C.; Li, M.; Guo, L. Green and facile synthesis of an Au nanoparticles@ polyoxometalate/ordered mesoporous carbon tri-component nanocomposite and its electrochemical applications. Biosens. Bioelectron. 2015, 66, 191−197. (2) Cheon, J. Y.; Ahn, C.; You, D. J.; Pak, C.; Hur, S. H.; Kim, J.; Joo, S. H. Ordered mesoporous carbon-carbon nanotube nanocomposites as highly conductive and durable cathode catalyst supports for polymer electrolyte fuel cells. J. Mater. Chem. A 2013, 1, 1270−1283. (3) Wang, J.; Huang, H.; Wang, M.; Yao, L.; Qiao, W.; Long, D.; Ling, L. Direct Capture of Low-Concentration CO2 on Mesoporous Carbon-Supported Solid Amine Adsorbents at Ambient Temperature. Ind. Eng. Chem. Res. 2015, 54, 5319−5327. (4) Liu, R.; Wan, L.; Liu, S.; Pan, L.; Wu, D.; Zhao, D. An InterfaceInduced Co-Assembly Approach Towards Ordered Mesoporous Carbon/Graphene Aerogel for High-Performance Supercapacitors. Adv. Funct. Mater. 2015, 25, 526−533. (5) Guo, Q.; Xue, Q.; Sun, J.; Dong, M.; Xia, F.; Zhang, Z. Gigantic Enhancement in the Dielectric Properties of Polymer-based Composites Using Core/Shell MWCNT/Amorphous Carbon Nanohybrids. Nanoscale 2015, 7, 3660−3667. (6) Chen, F.; Gong, A. S.; Zhu, M.; Chen, G.; Lacey, S. D.; Jiang, F.; Li, Y.; Wang, Y.; Dai, J.; Yao, Y.; Song, J.; Liu, B.; Fu, K.; Das, S.; Hu, L. Mesoporous, Three-Dimensional Wood Membrane Decorated with Nanoparticles for Highly Efficient Water Treatment. ACS Nano 2017, 11, 4275−4282. (7) Wang, Y.; Bai, X.; Wang, F.; Qin, H.; Yin, C.; Kang, S.; Li, X.; Zuo, Y.; Cui, L. Surfactant-assisted Nanocasting Route for Synthesis of Highly Ordered Mesoporous Graphitic Carbon and Its Application in CO2 Adsorption. Sci. Rep. 2016, 6, 26673−26679. (8) Fierro, C. M.; Górka, J.; Zazo, J. A.; Rodriguez, J. J.; Ludwinowicz, J.; Jaroniec, M. Colloidal templating synthesis and adsorption characteristics of microporous-mesoporous carbons from Kraft lignin. Carbon 2013, 62, 233−239. (9) Sun, Z.; Sun, B.; Qiao, M.; Wei, J.; Yue, Q.; Wang, C.; Deng, Y.; Kaliaguine, S.; Zhao, D. A General Chelate-Assisted Co-Assembly to Metallic Nanoparticles-Incorporated Ordered Mesoporous Carbon Catalysts for Fischer-Tropsch Synthesis. J. Am. Chem. Soc. 2012, 134, 17653−17660. (10) Li, J.; Gu, J.; Li, H.; Liang, Y.; Hao, Y.; Sun, X.; Wang, L. Synthesis of highly ordered Fe-containing mesoporous carbon
ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsomega.7b01870. XPS spectrum analysis (PDF) (PDF)
■
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail:
[email protected]. Phone/Fax: +86 21 65642789 (Q.F.Z.). *E-mail:
[email protected] (X.L.). ORCID
Xi Li: 0000-0002-5462-5159 1355
DOI: 10.1021/acsomega.7b01870 ACS Omega 2018, 3, 1350−1356
Article
ACS Omega materials using soft templating routes. Microporous Mesoporous Mater. 2010, 128, 144−149. (11) Ye, D.; Zhang, R.; Fu, Y.; Bu, J.; Wang, Y.; Liu, B.; Kong, J. Cocalcination-derived Pd budded in N-Doped Ordered Mesoporous Graphitic Carbon Nanospheres for Advanced Methanol-tolerant Oxygen Reduction. Electrochim. Acta 2015, 160, 306−312. (12) Wang, Y.; Zhao, H.; Zhao, G. Iron-copper bimetallic nanoparticles embedded within ordered mesoporous carbon as effective and stable heterogeneous Fenton catalyst for the degradation of organic contaminants. Appl. Catal., B 2015, 164, 396−406. (13) Wang, J.; Liu, H.; Diao, J.; Gu, X.; Wang, H.; Rong, J.; Zong, B.; Su, D. S. Size-controlled nitrogen-containing mesoporous carbon nanospheres by one-step aqueous self-assembly strategy. J. Mater. Chem. A 2015, 3, 2305−2313. (14) Xia, Q.; Chen, Z.; Shao, Y.; Gong, X.; Wang, H.; Liu, X.; Parker, S. F.; Han, X.; Yang, S.; Wang, Y. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes. Nat. Commun. 2016, 7, 11162. (15) Zhang, X.; Yan, Q.; Hassan, E. B.; Li, J.; Cai, Z.; Zhang, J. Temperature effects on formation of carbon-based nanomaterials from kraft lignin. Mater. Lett. 2017, 203, 42−45. (16) Qin, H.; Zhou, Y.; Bai, J.; Zhu, B.; Ni, Z.; Wang, L.; Liu, W.; Zhou, Q.; Li, X. Lignin-Derived Thin-Walled Graphitic CarbonEncapsulated Iron Nanoparticles: Growth, Characterization, and Applications. ACS Sustainable Chem. Eng. 2017, 5, 1917−1923. (17) Xu, L.; Yao, Q.; Zhang, Y.; Fu, Y. Integrated Production of Aromatic Amines and N-Doped Carbon from Lignin via ex Situ Catalytic Fast Pyrolysis in the Presence of Ammonia over Zeolites. ACS Sustainable Chem. Eng. 2017, 5, 2960−2969. (18) Kristianto, I.; Limarta, S. O.; Lee, H.; Ha, J.-M.; Suh, D. J.; Jae, J. Effective depolymerization of concentrated acid hydrolysis lignin using a carbon-supported ruthenium catalyst in ethanol/formic acid media. Bioresour. Technol. 2017, 234, 424−431. (19) Zhai, Y.; Li, C.; Xu, G.; Ma, Y.; Liu, X.; Zhang, Y. Depolymerization of lignin via a non-precious Ni-Fe alloy catalyst supported on activated carbon. Green Chem. 2017, 19, 1895−1903. (20) Zhang, L.; You, T.; Zhou, T.; Zhou, X.; Xu, F. Interconnected Hierarchical Porous Carbon from Lignin-Derived Byproducts of Bioethanol Production for Ultra-High Performance Supercapacitors. ACS Appl. Mater. Interfaces 2016, 8, 13918−13925. (21) Klose, M.; Reinhold, R.; Logsch, F.; Wolke, F.; Linnemann, J.; Stoeck, U.; Oswald, S.; Uhlemann, M.; Balach, J.; Markowski, J.; Ay, P.; Giebeler, L. Softwood Lignin as a Sustainable Feedstock for Porous Carbons as Active Material for Supercapacitors Using an Ionic Liquid Electrolyte. ACS Sustainable Chem. Eng. 2017, 5, 4094−4102. (22) Qin, H.; Wang, B.; Zhang, C.; Zhu, B.; Zhou, Y.; Zhou, Q. Lignin based synthesis of graphitic carbon-encapsulated iron nanoparticles as effective catalyst for forming lower olefins via FischerTropsch synthesis. Catal. Commun. 2017, 96, 28−31. (23) Jeon, J.-W.; Zhang, L.; Lutkenhaus, J. L.; Laskar, D. D.; Lemmon, J. P.; Choi, D.; Nandasiri, M. I.; Hashmi, A.; Xu, J.; Motkuri, R. K.; Fernandez, C. A.; Liu, J.; Tucker, M. P.; McGrail, P. B.; Yang, B.; Nune, S. K. Controlling Porosity in Lignin-Derived Nanoporous Carbon for Supercapacitor Applications. ChemSusChem 2015, 8, 428− 432. (24) Laskar, D. D.; Tucker, M. P.; Chen, X.; Helms, G. L.; Yang, B. Noble-metal catalyzed hydrodeoxygenation of biomass-derived lignin to aromatic hydrocarbons. Green Chem. 2014, 16, 897−910. (25) Wang, Y.; Li, B.; Zhang, C.; Song, X.; Tao, H.; Kang, S.; Li, X. A simple solid-liquid grinding/templating route for the synthesis of magnetic iron/graphitic mesoporous carbon composites. Carbon 2013, 51, 397−403. (26) Wang, Q.; Zhang, W.; Mu, Y.; Zhong, L.; Meng, Y.; Sun, Y. Synthesis of ordered mesoporous carbons with tunable pore size by varying carbon precursors via soft-template method. Microporous Mesoporous Mater. 2014, 197, 109−115. (27) Qu, Y.; Zhang, Z.; Zhang, X.; Ren, G.; Lai, Y.; Liu, Y.; Li, J. Highly ordered nitrogen-rich mesoporous carbon derived from biomass waste for high-performance lithium-sulfur batteries. Carbon 2015, 84, 399−408.
(28) Saha, D.; Li, Y.; Bi, Z.; Chen, J.; Keum, J. K.; Hensley, D. K.; Grappe, H. A.; Meyer, H. M.; Dai, S.; Paranthaman, M. P.; Naskar, A. K. Studies on Supercapacitor Electrode Material from Activated Lignin-Derived Mesoporous Carbon. Langmuir 2014, 30, 900−910. (29) Song, J.; Kahveci, D.; Chen, M.; Guo, Z.; Xie, E.; Xu, X.; Besenbacher, F.; Dong, M. Enhanced Catalytic Activity of Lipase Encapsulated in PCL Nanofibers. Langmuir 2012, 28, 6157−6162. (30) Zhang, M.; Sun, A.; Meng, Y.; Wang, L.; Jiang, H.; Li, G. High activity ordered mesoporous carbon-based solid acid catalyst for the esterification of free fatty acids. Microporous Mesoporous Mater. 2015, 204, 210−217. (31) Al-Sayari, S. A. Catalytic conversion of syngas to olefins over Mn-Fe catalysts. Ceram. Int. 2014, 40, 723−728. (32) Galvis, H. M. T.; Bitter, J. H.; Khare, C. B.; Ruitenbeek, M.; Dugulan, A. I.; de Jong, K. P. Supported Iron Nanoparticles as Catalysts for Sustainable Production of Lower Olefins. Science 2012, 335, 835−838. (33) Fan, Z.; Chen, W.; Pan, X.; Bao, X. Catalytic conversion of syngas into C2 oxygenates over Rh-based catalysts-Effect of carbon supports. Catal. Today 2009, 147, 86−93.
1356
DOI: 10.1021/acsomega.7b01870 ACS Omega 2018, 3, 1350−1356
