Large-scale synthesis of 3D ordered microporous carbon at low temperature using cobalt ions exchanged zeolite Y as a template
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摘要: 沸石模板炭（ZTCs）由于具有独特的三维有序微孔结构和高比表面积，在吸附和能量存储等方面表现出诸多优异的性能。然而，ZTCs有效合成方法的缺乏和大规模合成的困难严重限制其发展。本文通过使用钴离子交换的Y型沸石分子筛作为模板，采用直接乙炔化学气相沉积（CVD）的方法，开发出一种低温CVD合成及宏量制备ZTCs的简单工艺路线。沸石中的钴离子作为Lewis酸位点，通过d-π配位效应催化乙炔在400 °C低温热解，使碳沉积选择性地发生在沸石内部。通过对CVD温度和时间的优化，ZTC(Co)-400-8h具有优异的三维有序微孔结构、高比表面积（3000 m2 g−1）、大的孔体积（1.33 cm3 g−1），CO2吸附容量和选择性分别为2.78 mmol g−1（25°C，100 kPa）和98。本工作中，利用简单的合成方法实现了高质量ZTCs的宏量制备，使用10.0 g/批次沸石模板制备的ZTC(Co)-400-8h(L)的比表面和孔体积可达到2700 m2 g−1和1.27 cm3 g−1。Abstract: Zeolite-templated carbons (ZTCs) have a unique three-dimensional (3D) ordered microporous structure and an extra-large surface area, and have excellent properties in adsorption and energy storage. Unfortunately, the lack of efficient synthesis strategies and the difficulty of doing this on a large-scale have seriously limited their development. We have developed a large-scale simple production route using a relatively low synthesis temperature and direct acetylene chemical vapor deposition (CVD) using Co ion-exchanged zeolite Y (CoY) as the template. The Co2+ confined in the zeolite acts as Lewis acid sites to catalyze the pyrolysis of acetylene through the d-π coordination effect, making carbon deposition occur selectively inside the zeolite at 400 °C rather than on the external surface. By systematically investigating the CVD temperature and time, the optimum conditions of 8 h deposition at 400 °C produces an excellent 3D ordered-microporous structure and outstanding structure parameters (3 000 m2 g−1, 1.33 cm3 g−1). Its CO2 adsorption capacity and selectivity are 2.78 mmol g−1 (25 °C, 100 kPa) and 98, respectively. This simple CVD process allows the synthesis of high-quality ZTCs on a large scale at a low cost.
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1. Schematic diagram for the synthesis of ZTC(Co) and in-situ CNTs/ ZTC(Co) by using CoY zeolite as a template and acetylene as a carbon source
Figure 1. (a) XPS survey spectra of the NaY and CoY zeolite. (b) Small-angle and (c) wide-angle XRD patterns of the NaY zeolite, CoY zeolite (before calcination) and CoY zeolite. (d-f) SEM images of NaY zeolite, CoY zeolite (before calcination) and CoY zeolite, respectively
Figure 2. (a) Amount of carbon deposition in the NaY and CoY zeolite plotted as a function of the different temperatures with using acetylene/Ar gas for 1 h. (b) Small-angle and (c) wide-angle XRD patterns of all ZTC(Co)-A-1h samples. SEM images: (d) Secondary electron and (e, f) back scattered electron images of ZTC(Co)-400-1h
Figure 3. (a) N2 adsorption-desorption isotherms and (b) NLDFT pore size distribution of different ZTC(Co)-A-1h samples
Figure 4. (a) TGA curves of C/CoY-400-1h, C/CoY-400-2h, C/CoY-400-4h and C/CoY-400-8h. (b) Small-angle XRD patterns, (c) N2 adsorption-desorption isotherms and (d) NLDFT pore size distribution of ZTC(Co)-400-1h, ZTC(Co)-400-2h, ZTC(Co)-400-4h and ZTC(Co)-400-8h
Figure 5. (a, b) SEM images of ZTC(Co)-400-8h, (c, d) TEM images of ZTC(Co)-400-8h with different viewing directions
Figure 6. (a-d) CO2 adsorption isotherms (0, 25 and 50 °C) and N2 adsorption isotherms (25 °C, black hollow circular). (e) Comparison of CO2 adsorption properties at 25 °C. (f) Analysis of the plot of CO2 adsorption capacity, specific surface area (red), and total pore volume (blue). (g) Isosteric heat of CO2 adsorption (Qst). (h) Pore size distribution (0.4-1.0 nm) derived from CO2 adsorption isotherm (0 °C) by NLDFT method. (i) CO2/N2 selectivity calculated using IAST at 25 °C
Figure 7. (a-e) Photographs of quartz reactor for large-scale synthesis filled with a thick bed of CoY zeolite (10.0 g) sample. (f) XRD pattern of ZTC(Co)-400-8h(L)
Table 1. The SSA and pore volume from the N2 adsorption-desorption isotherms at −196 °C and synthesis condition for ZTC(Co)-400-B
Samples Timea SSAb V1c V2d ZTC(Co)-400-1h 1 2200 1.00 0.80 ZTC(Co)-400-2h 2 2390 1.05 0.82 ZTC(Co)-400-4h 4 2520 1.11 0.87 ZTC(Co)-400-8h 8 3000 1.33 1.03 Note-Timea: CVD time (h), SSAb: BET specific surface area, m2 g−1, V1c: total pore volume, cm3 g−1, V2 d: micropore volume, cm3 g−1. 
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[1] Iijima S. Helical microtubules of graphitic carbon[J]. Nature,1991,354:56-58. doi: 10.1038/354056a0 [2] Geim A K. Graphene: status and prospects[J]. Science,2009,324:1530-1534. [3] Wang A M, Ren J W, Shi B F, et al. A facile one-pot synthesis of mesoporous graphite-like carbon through the organic-organic co-assembly[J]. Microporous and Mesoporous Materials,2012,151(15):287-292. [4] Liu W L, Du L Y, Ju S L, et al. Encapsulation of red phosphorus in carbon nanocages with ultrahigh content for high-capacity and long cycle life sodium-ion batteries[J]. ACS Nano,2021,15(3):5679-5688. doi: 10.1021/acsnano.1c00924 [5] Liu L, Kan Y Y, Gao K, et al. Graphdiyne derivative as multifunctional solid additive in binary organic solar cells with 17. 3% efficiency and high reproductivity[J]. Advanced Materials,2020,32(11):1907604. doi: 10.1002/adma.201907604 [6] Zhao H W, Xing T Y, Li L X, et al. Synthesis of cobalt and nitrogen co-doped carbon nanotubes and its ORR activity as the catalyst used in hydrogen fuel cells[J]. International Journal of Hydrogen Energy,2019,44(44):25180-25187. [7] An B G, Xu S F, Li L X, et al. Carbon nanotubes coated with a nitrogen-doped carbon layer and its enhanced electrochemical capacitance[J]. Journal of Materials Chemistry A,2013,1(24):7222-7228. doi: 10.1039/c3ta10830a [8] Mauter M S, Elimelech M. Environmental applications of carbon-based nanomaterials[J]. Environmental Science & Technology,2008,42(16):5843-5859. [9] Graboski A M, Zakrzevski C A, Shimizu F M, et al. Electronic nose based on carbon nanocomposite sensors for clove essential oil detection[J]. ACS Sensors,2020,5(6):1814-1821. doi: 10.1021/acssensors.0c00636 [10] Zhu C Y, Ye Y W, Guo X, et al. Design and synthesis of carbon-based nanomaterials for electrochemical energy storage[J]. New Carbon Materials,2022,37(1):59-92. [11] Zhou Y, Jia Z X, Zhao S Y, et al. Construction of triple-shelled hollow nanostructure by confining amorphous Ni-Co-S/crystalline MnS on/in hollow carbon nanospheres for all-solid-state hybrid supercapacitors[J]. Chemical Engineering Journal,2021,416(15):129500. [12] Li X Y, Sari H M K, Niu L J, et al. Porous graphene nanocages with wrinkled surface enhancing electrocatalytic activity of lithiun/sulfuryl chloride batteries[J]. RSC Advances,2021,11(16):9469-9475. doi: 10.1039/D0RA10756E [13] Zhang X L, Ruan Z Q, He Q T, et al. Three-dimensional (3D) nanostructure skeleton substrate composed of hollow carbon fiber/carbon nanosheet/ZnO for stable lithium anode[J]. ACS Applied Materials & Interfaces,2021,13(2):3078-3088. [14] Cheng H Y, Cheng P Y, Chuah X F, et al. Porous N-doped carbon nanostructure integrated with mesh current collector for Li-ion based energy storage[J]. Chemical Engineering Journal,2019,374(15):201-210. [15] Zhao H W, Zhang Y Q, Li L X, et al. Synthesis of an ordered porous carbon with the dual nitrogen-doped interface and its ORR catalysis performance[J]. Chinese Chemical Letters,2021,32(1):140-145. doi: 10.1016/j.cclet.2020.11.035 [16] Zhu Y, Miyake K, Shu Y, et al. Single atomic Co coordinated with N in microporous carbon for oxygen reduction reaction obtained from Co/2-methylimidazole anchored to Y zeolite as a template[J]. Materials Today Chemistry,2021,20:100410. doi: 10.1016/j.mtchem.2020.100410 [17] Konnov S V, Dubray F, Clatworthy E B, et al. Novel strategy for the synthesis of ultra-stable single-site Mo-ZSM-5 zeolite nanocrystals[J]. Angewandte Chemie International Edition,2020,59(44):19553-19560. doi: 10.1002/anie.202006524 [18] Cui X X, Xu Y S, Chen L L, et al. Ultrafine Pd nanoparticles supported on zeolite-templated mesocellular graphene network via framework aluminum mediation: an advanced oxygen reduction electrocatalyst[J]. Applied Catalysis B:Environmental,2019,244:957-964. doi: 10.1016/j.apcatb.2018.12.026 [19] Nueangnoraj K, Ruiz-Rosas R, Nishihara H, et al. Carbon–carbon asymmetric aqueous capacitor by pseudocapacitive positive and stable negative electrodes[J]. Carbon,2014,67:792-794. doi: 10.1016/j.carbon.2013.10.011 [20] Nomura K, Nishihara H, Yamamoto M, et al. Force-driven reversible liquid–gas phase transition mediated by elastic nanosponges[J]. Nature Communications,2019,10:2559. doi: 10.1038/s41467-019-10511-7 [21] Tang R, Taguchi K, Nishihara H, et al. Insight into the origin of carbon corrosion in positive electrodes of supercapacitors. Journal of Materials Chemistry A, 2019, 7(13): 7480-7488. [22] Dubey R J C, Nüssli J, Piveteau L, et al. Zeolite-templated carbon as the cathode for a high energy density dual-ion battery[J]. ACS Applied Materials & Interfaces,2019,11(19):17686-17696. [23] Itoi H, Nishihara H, Kogure T, et al. Three-dimensionally arrayed and mutually connected 1. 2-nm nanopores for high-performance electric double layer capacitor[J]. Journal of the American Chemical Society,2011,133(5):1165-1167. doi: 10.1021/ja108315p [24] Choi S, Kim H, Lee S, et al. Large-scale synthesis of high-quality zeolite-templated carbons without depositing external carbon layers[J]. Chemical Engineering Journal,2015,280(15):597-605. [25] Nishihara H, Kyotani T. Zeolite-templated carbons-three-dimensional microporous graphene frameworks[J]. Chemical Communications,2018,54(45):5648-5673. doi: 10.1039/C8CC01932K [26] Kyotani T, Nagai T, Inoue S, et al. Formation of new type of porous carbon by carbonization in zeolite nanochannels[J]. Chemistry of Materials,1997,9(2):609-615. doi: 10.1021/cm960430h [27] Matsuoka K, Yamagishi Y, Yamazaki T, et al. Extremely high microporosity and sharp pore size distribution of a large surface area carbon prepared in the nanochannels of zeolite Y[J]. Carbon,2005,43(3):876-879. [28] Ma Z X, Kyotani T, Tomita Akira. Preparation of a high surface area microporous carbon having the structural regularity of Y zeolite[J]. Chemical Communication, 2000, 2365-2366. [29] Ma Z X, Kyotani T, Tomita Akira. Synthesis methods for preparing microporous carbons with a structural regularity of zeolite Y[J]. Carbon,2002,40(13):2367-2374. doi: 10.1016/S0008-6223(02)00120-3 [30] Hou P X, Yamazaki T, Orikasa H, et al. An easy method for the synthesis of ordered microporous carbons by the template technique[J]. Carbon,2005,43(12):2624-2627. doi: 10.1016/j.carbon.2005.05.001 [31] Zhao H W, Li L X, Liu Y Y, et al. Synthesis and ORR performance of nitrogen-doped ordered microporous carbon by CVD of acetonitrile vapor using silanized zeolite as template[J]. Applied Surface Scienve,2020,504(28):144438. [32] Kim K, Lee T, Kwon Y, et al. Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template[J]. Nature,2016,535:131-135. doi: 10.1038/nature18284 [33] Kim K, Kwon Y, Lee Y, et al. Facile large-scale synthesis of three-dimensional graphene-like ordered microporous carbon via ethylene carbonization in CaX zeolite template[J]. Carbon 2017, 118: 517-523. [34] Moon G H, Bähr A, Tüysüz H. Structural engineering of 3D carbon materials from transition metal ion-exchanged Y zeolite templates[J]. Chemistry of Materials,2018,30(11):3779-3788. doi: 10.1021/acs.chemmater.8b00861 [35] Han J, Zhang L, Zhao B, et al. The N-doped activated carbonderived from sugarcane bagasse for CO2 adsorption[J]. Industrial Crops and Products,2019,128:290-297. doi: 10.1016/j.indcrop.2018.11.028 [36] Bhadra B N, Seo P W, Jhung S H. Adsorption of diclofenac sodium from water using oxidized activated carbon[J]. Chemical Engineering Journal,2016,301(1):27-34. [37] Jin Q Q, Fang D, Ye Y L, et al. Cu, Co, or Ni species in exchanged Y zeolite catalysts and their denitration performance for selective catalytic reduction by ammonia[J]. Applied Surface Science,2022,600(30):154075. [38] Shilina M I, Rostovshchikova T N, Nikolaev S A, et al. Polynuclear Co-oxo cations in the catalytic oxidation of CO on Co-modified ZSM-5 zeolites[J]. Materials Chemistry and Physics,2019,223(1):287-298. [39] Balahmar N, Lowbridge A M, Mokaya R. Templating of carbon in zeolites under pressure: synthesis of pelletized zeolite templated carbons with improved porosity and packing density for superior gas (CO2 and H2) uptake properties[J]. Journal of Materials Chemistry A,2016,4(37):14254-14266. doi: 10.1039/C6TA06176A [40] Nishihara H, Ittisanronnachai S, Itoi H, et al. Experimental and theoretical studies of hydrogen/deuterium spillover on Pt-loaded zeolite-templated carbon[J]. The Journal of Physical Chemistry C,2014,118(18):9551-9559. doi: 10.1021/jp5016802 [41] Konwar R J, De M. Effects of synthesis parameters on zeolite templated carbon for hydrogen storage application[J]. Microporous and Mesoporous Materials,2013,175(15):16-24. [42] Ania C O, Khomenko V, Raymundo-Piñero E, et al. The large electrochemical capacitance of microporous doped carbon obtained by using a zeolite template[J]. Advanced Functional Materials,2007,17(11):1828-1836. doi: 10.1002/adfm.200600961 [43] Yang Z X, Xia Y D, Mokaya R. Hollow shells of high surface area graphitic N-doped carbon composites nanocast using zeolite templates[J]. Microporous and Mesoporous Materials,2005,86(1-3):69-80. doi: 10.1016/j.micromeso.2005.05.055 [44] Eveleens C A, Irle S, Page A J. How does acetonitrile modulate single-walled carbon nanotube diameter during CVD growth[J]. Carbon,2019,146:535-541. doi: 10.1016/j.carbon.2019.02.027 [45] Miao Z C, Meng J, Liang M F, et al. In-situ CVD synthesis of Ni@N-CNTs/carbon paper electrode for electro-reduction of CO2[J]. Carbon,2021,172:324-333. doi: 10.1016/j.carbon.2020.10.044 [46] Itoi H, Kasai Y, Morishita K, et al. Facile synthesis of high surface area zeolite-templated carbons using divinyblenzene and propylene as carbon sources[J]. Microporous and Mesoporous Materials,2021,326:111378. doi: 10.1016/j.micromeso.2021.111378 [47] Zaretskiy S N, Hong Y K, Ha D H, et al. Growth of carbon nanotubes from Co nanoparticles and C2H2 by thermal chemical vapor deposition[J]. Chemical Physics Letters,2003,372(1-2):300-305. doi: 10.1016/S0009-2614(03)00405-6 [48] Nishihara H, Fujimoto H, Itoi H, et al. Graphene-based ordered framework with a diverse range of carbon polygons formed in zeolite nanochannels[J]. Carbon,2018,129:854-862. doi: 10.1016/j.carbon.2017.12.055 [49] Madison L, Heitzer H, Russell C, et al. Atomistic simulations of CO2 and N2 within cage-type silica zeolites[J]. Langmuir,2011,27(5):1954-1963. doi: 10.1021/la104245c [50] Mehio N, Dai S, Jiang D. Quantum mechanical basis for kinetic diameters of small gaseous molecules[J]. The Journal of Physical Chemistry A,2014,118(6):1150-1154. doi: 10.1021/jp412588f [51] Sakamoto H, Fujimori T, Li X L, et al. Cycloparaphenylene as a molecular porous carbon solid with uniform pores exhibiting adsorption-induced softness[J]. Chemical Science,2016,7(7):4204-4210. doi: 10.1039/C6SC00092D [52] Zhang Y Y, Zhang S N, Wang Z C, et al. Determination of the absolute CH4 adsorption using simplified local density theory and compariosn with the modified Langmuir adsorption model[J]. RSC Advances,2018,8(72):41509-41516. doi: 10.1039/C8RA08586B [53] Li H J, Wang S C, Zeng Q, et al. Effects of pore structure of different rank coals on methane adsorption heat[J]. Processes,2021,9(11):1971. doi: 10.3390/pr9111971 [54] García-Díez E, Castro-Muñiz A, Paredes J I, et al. CO2 capture by novel hierarchical activated ordered micro-mesoporous carbons derived from low value coal tar products[J]. Microporous and Mesoporous Materials,2021,318:110986. doi: 10.1016/j.micromeso.2021.110986 [55] Wang X J, Yuan B Q, Zhou X, et al. Novel glucose-based adsorbents (Glc-Cs) with high CO2 capacity and excellent CO2/CH4/N2 adsorption selectivity[J]. Chemical Engineering Journal,2017,327:51-59. doi: 10.1016/j.cej.2017.06.074 [56] Li D, Chen Y L, Zheng M, et al. Hierarchically structured porous nitrogen-doped carbon for highly selective CO2 capture[J]. ACS Sustainable Chemistry & Engineering,2016,4(1):298-304. [57] Kim Y K, Kim G M, Lee J W. Highly porous N-doped carbons impregnated with sodium for efficient CO2 capture[J]. Journal of Materials Chemistry A,2015,3(20):10919-10927. doi: 10.1039/C5TA01776A -
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