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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