掺氮多孔碳在二氧化碳吸附分离中的应用

doi:10.15541/jim20140175

摘要/Abstract

摘要：

CO₂作为温室气体, 其捕集和存储有着重要的现实意义。多孔碳材料掺杂N原子后可以极大地改变材料的表面化学性质, 增强表面碱性, 在CO₂吸附领域具有广泛的应用。基于N掺杂最新研究进展, 本文系统地介绍了原位、后处理等掺N方法和不同孔道结构对CO₂吸附分离或扩散传质的影响, 总结归纳了材料的物理结构参数、表面化学性质与CO₂吸附分离性能的关系, 指出了各种制备方法存在的问题及解决的方法, 为高性能的CO₂吸附剂的定向设计、制备以及工业化提供了理论参考。

关键词: 多孔碳, 氮掺杂, CO2吸附, 综述

Abstract:

CO₂is regarded as a greenhouse gas. Its capture and storage has important practical significance. Porous carbon materials doped with N atoms can greatly change the surface chemical properties, strengthen basic surface, which have wide application in the field of CO₂ adsorption. In this paper, based on the latest research progresses of N-doped carbon materials, the direct synthesis, post treatment strategies, etc. and pore structure of N-doped porous carbon for adsorption, separation or diffusion of CO₂ were introduced in detail. The relationships between the physical structure parameters, surface chemistry of N-doped carbon materials and CO₂ adsorption separation performance were systematically summarized. It was also pointed out the existing problems and the solutions of various treatment methods. Preparation and industrialization of high performance CO₂ adsorbents provide theoretical support for the directional design.

Key words: porous carbon, N-doping, CO2 adsorption, review

中图分类号:

O613

陈爱兵, 于奕峰, 臧文伟, 齐国禄, 于运红, 李月彤. 掺氮多孔碳在二氧化碳吸附分离中的应用[J]. 无机材料学报, 2015, 30(1): 9-16.

CHEN Ai-Bing, YU Yi-Feng, ZANG Wen-Wei, QI Guo-Lu, YU Yun-Hong, LI Yue-Tong. Nitrogen-doped Porous Carbon for CO₂ Adsorption[J]. Journal of Inorganic Materials, 2015, 30(1): 9-16.

图/表 7

图 1 N原子在碳材料中的可能存在形式示意图[9]

Fig. 1 Possible positions of N atom in the carbon materials [9].(1-Anmio-N; 2-Pyrrolic; 3-Nitrosyl-N; 4-Pyridone; 5-Quaternary)

图2 EISA法添加双腈胺制备碳材料的合成机理图(a)及CO2/N2选择性吸附图(b)[16]

Fig. 2 Formation process of N-doped mesoporous carbon using dicyandiamide as an additive (a); CO2 and N2 adsorption isotherms (b)[16]

图 3 高压下[BMIm][C(CN)3]/[EMIm][B(CN)4]=1:2碳混合样品的CO2、N2吸附-脱附等温曲线[17]

Fig. 3 CO2 and N2 adsorption-desorption isotherms as a function of pressure of the carbons from [BMIm] [C(CN)3]/ [EMIm] [B(CN)4]=1:2[17]

图 4 CO2吸附量与氮掺杂和未氮掺杂的碳材料比表面积关系(1.013×105 Pa, 298 K), 氮含量在6wt%~7wt%[26]

Fig. 4 Relationships between the CO2 adsorption capacities (at 298 K and 1 .013×105 Pa) and the BET surface area of nitrogen- doped and undoped carbons. The N-doped carbons contain 6wt%-7wt% N[26]

图 5 介孔碳泡沫的合成示意图(a)和75℃下PEI浸渍介孔碳泡沫的CO2吸附动力学曲线(b)[35]

Fig. 5 Schematic illustration of the synthesis method of mesoporous carbon foams(a) and CO2 adsorption kinetics of the PEI-impregnated mesoporous carbon sorbent at 75℃(b)[35]

图 6 分级整块碳材料的SEM照片、N2吸附-脱附曲线和孔径分布图(a~d)和(e)光学照片[46]

Fig. 6 SEM images of hierarchical porous carbon and N2 adsorption-desorption and PSD (a-d) and optical images (e)[46]

表 1 不同掺氮碳材料对CO2的吸附能力比较

Table 1 Different nitrogen doped carbon materials for CO2 adsorption capacity

Samples	Nitrogen source	Nitrogen content/wt%	Functionalities	Surface area /(m²·g^-1)	CO₂ capacity /(mmol·g^-1)
N-doped microporous carbon^[48]	Imine-linked polymer	5.58-8.74	Pyridinic, quaternary	263-366	1.95
N-doped mesoporous carbon^[49]	Melamine resin	-8.00	Pyridinic, pyrrolic, quaternary	-750	1.80
KOH activated porous carbon^[13]	Polypyrrole	-10.14	Pyridinic,quaternary	1700	3.10
Organic amine grafting carbon^[50]	Glucose	NA	Amide, tertiary amines, primary amines	<10	4.10
Macro-micro hollow carbon spheres^[51]	Melamine	14.80	NA	767	2.67
Sustainable biomass^[38]	Glgae	1.1-4.7	Pyridinic, pyrrolic, quaternary	1300-2400	7.40
Template carbon^[52]	HNO₃	6.73	Pyridinic, pyrrolic, quaternary	1979	4.30
N-doped activated carbon monoliths^[11]	Polyacrylonitrile	1.80	NA	2501	5.14

参考文献 52

[1]	ROCHELLE G T.Amine scrubbing for CO2 capture. Science, 2009, 325(5948):1652-1654.
[2]	CHOMAA J, JEDYNAKB K, JARONIECC M, et al.Microporosity development in phenolic resin-based mesoporouscarbons for enhancing CO2 adsorption at ambient conditions.Applied Surface Science, 2014, 289(2): 592-600.
[3]	LUO J, PENG F, ZHENG W X, et al.Aerobic liquid-phase oxidation of ethyl benzene to acetophenone catalyzed by carbon nanotubes.ChemCatChem, 2013, 5(6):1578-1586.
[4]	ALAM N, MOKAYA R, Evolution of optimal porosity for improved hydrogen storage in template zeolite-like carbons.Energy Environ. Sci., 2010, 3(11): 1773-1781.
[5]	WANG J X, XUE C F, LV Y Y, et al.Kilogram-scale synthesis of ordered mesoporous carbons and their electrochemical performance.Carbon, 2011; 49(13): 4580-4588.
[6]	CHANG H, JOO S H, PAK C.Synthesis and characterization of mesoporouscarbonfor fuel cell applications. J. Mater. Chem., 2007, 17(30): 3078-3088.
[7]	WU Z X, PAUL A, ZHAO D Y, et.al. Post-enrichment of nitrogen in soft-templated ordered mesoporouscarbonmaterials for highly efficient phenol removal and CO2 capture.J. Mater. Chem., 2012, 22(22):11379-11389.
[8]	LIU L, DENG Q F, YUAN Z Y, et.al. Ordered mesoporous carbons: citric acid-catalyzed synthesis, nitrogen doping and CO2 capture.J. Mater. Chem., 2011, 21(40): 16001-16009.
[9]	WANG X Q, LIU C G, DAI S, et al.Nitrogen-enriched ordered mesoporous carbons through direct pyrolysis in ammonia with enhanced capacitive performance. J. Mater. Chem. A, 2013, 1(27):7920-7926.
[10]	DARGE T C, ARENILLA S A, SNAPE C E.Preparation of carbon dioxide adsorbents from the chemical activation of urea- formaldehyde and melamine-formaldehyde resins.Fuel, 2007, 86(1/2): 22-31.
[11]	NANDI M, OKADA K, UYAMA D H.Unprecedented CO2 uptake over highly porous N-doped activated carbon monoliths prepared by physical activation.Chem. Commun., 2012, 48(83): 10283-10285.
[12]	ZHAO Y F, ZHAO L, HAN Y, et al.Novel porous carbon materials with ultrahigh nitrogen contents for selective CO2 capture.J. Mater. Chem., 2012, 22(37): 19726-19731.
[13]	SEVILLA M, VIGÓN P V, FUERTES A B. N-doped polypyrrole-based porous carbons for CO2capture.Adv. Funct. Mater., 2011, 21(14): 2781-2787.
[14]	YU J Y, GUO M Y, ZHU G S, et al.One-pot synthesis of highly ordered nitrogen-containing mesoporous carbon with resorcinol-urea-formaldehyde resin for CO2 capture.Carbon, 2014, 69(4): 502-514.
[15]	FENG C M, LI H X, WAN Y.Fabrication of N-doped highly ordered mesoporous polymers and carbons.J. Nanosci. Nanotechnol, 2009, 9(2):1558-1563.
[16]	WEI J, ZHOU D D, ZHAO D Y, et al.A Controllable synthesis of rich nitrogen-doped ordered mesoporous carbon for CO2 capture and supercapacitors. Adv. Funct. Mater., 2013, 23(18): 2322-2328.
[17]	FULVIO P F, LEE J S, DAI S, et al.Boron and nitrogen-rich carbons from ionic liquid precursors with tailorable surface properties.Phys. Chem. Chem. Phys., 2011, 13(30): 13486-13491.
[18]	CHEN A B, YU Y F, LV H J, et al.Thin-walled, mesoporous and nitrogen-doped hollow carbon spheres using ionic liquids as precursors.J. Mater. Chem., 2013, 1(4): 1045-1047.
[19]	CHEN A B, LIU C, YU Y F, et al.A co-confined carbonization approach to aligned nitrogen-doped mesoporous carbon nanofibers and its application as an adsorbent.J. Hazard. Mater., 2014, 276(13): 192-199.
[20]	PLAZA M G, PEVIDA C, ARENILLAS A, et al.CO2 capture by adsorption with nitrogen enriched carbons.Fuel, 2007, 86(14): 2204-2212.
[21]	SONG J, SHEN W Z, WANG J G, et al.Superior carbon-based CO2 adsorbents prepared from poplar anthers.Carbon, 2014, 69(4): 255-263.
[22]	SAYARI A, BELMABKHOUT Y.Stabilization of amine- containing CO2 adsorbents: dramatic effect of water vapor. J. Am. Chem. Soc., 2010, 132(18): 6312-6314.
[23]	WANG J C, LIU Q.An efficient one-step condensation and activationstrategy to synthesize porous carbons with optimal micropore sizes for highly selective CO2 adsorption.Nanoscale, 2014, 6(8): 4148-4156.
[24]	ZHANG Z.S, ZHOU J, QIAO S Z, et al. Critical role of small micropores in high CO2 uptake.Phys. Chem. Chem. Phys., 2013, 15(7): 2523-2529.
[25]	ZHOU J, LI W, ZHUO S P, et al.Carbon dioxide adsorption performance of N-doped zeolite Y template carbons.RSC Adv., 2012, 2(1): 161-167.
[26]	WANG L, YANG R T.Significantly increased CO2 adsorption performance of nanostructured templated carbon by tuning surface area and nitrogen doping.J. Phys. Chem. C, 2012, 116(1): 1099-1106.
[27]	MANGUN C L, BENAK K R, ECONOMY J, et al.Surface chemistry, pore sizes and adsorption properties of activated carbon fibers and precursors treated with ammonia. Carbon, 2001, 39(12): 1809-1820.
[28]	SHEN W Z, ZHANG S C, FAN W B, et al.Hierarchical porous polyacrylonitrile-based activated carbon fibers for CO2 capture.J. Mater. Chem., 2011, 21(36): 14036-14040.
[29]	HAO G P, JIN Z Y, LU A H.Porous carbon nanosheets with precisely tunablethickness and selective CO2 adsorption properties.Energy Environ. Sci., 2013, 6(12): 3740-3747.
[30]	CHANDRA V, YU S U, KIM K S, et al.Highly selective CO2 capture on N-doped carbon produced by chemicalactivation of polypyrrole functionalized graphene sheets.Chem. Commun., 2012, 48(5): 735-737.
[31]	SHEN Y M, BAI J F.A new kind CO2/CH4 separation material: open ended nitrogen doped carbon nanotubes formed by direct pyrolysis of metal organicframeworks.Chem. Commun., 2010, 46(8): 1308-1310.
[32]	ZHAO Y X, SEREDYCH M, BANDOSZ T J.Superior performance of copper based MOF and aminatedgraphite oxide composites as CO2 adsorbents at room temperature.ACS Appl. Mater Interfaces, 2013, 5(11): 4951-4959.
[33]	BABARAO R, DAI S, JIANG D E.Nitrogen-doped mesoporouscarbon for carbon capture-a molecular simulation study.J. Phys. Chem. C, 2012, 116(12):7106-7110.
[34]	YU J Y, GUO M Y, ZHU G S, et al.Simple fabrication of an ordered nitrogen-doped mesoporous carbon with resorcinol- melamine-formaldehyde resin.Microporous Mesoporous Mater., 2014, 190(8): 117-127.
[35]	FU L L, QI G G, GIANNELIS E P, et al.Facile synthesis and application of a carbon foam with large mesopores.Phys. Chem. Chem. Phys., 2013, 15(44): 19134-19137.
[36]	WHITE R J, ANTONIETTI M, TITIRICI M M, et al.Naturally inspired nitrogen doped porous carbon. J. Mater. Chem., 2009, 19(45): 8645-8650.
[37]	OLEJNICZAK A, LEZANSKA M, LUKASZEWICZA J P, et al.Novel nitrogen-containing mesoporous carbons prepared from chitosan.J. Mater. Chem. A, 2013, 1(31): 8961-8967.
[38]	SEVILLA M, FALCO C, FUERTES A B, et al.High-performance CO2 adsorbents from algae.RSC Adv., 2012, 2(33): 12792-12797.
[39]	WOOD K N, HAYREA R O, PYLYPENKO S.Recent progress on nitrogen·carbon structures designed for use in energy and sustainability applications.Energy Environ. Sci., 2014, 7: 1212-1249.
[40]	WANG J C, LIU Q.An ordered mesoporous aluminosilicateoxynitridetemplate to prepare N-incorporated ordered mesoporous carbon.J. Phys. Chem. C, 2007, 111(20): 7266-7272.
[41]	YANG H W, YUAN Y Z, EDMAN TSANG S C. Nitrogen- enriched carbonaceous materials with hierarchical micro-mesopore structures for efficient CO2 capture. Chemical Engineering Journal, 2012, 185-186(5): 374-379.
[42]	LI Q, YANG J P, ZHAO D Y, et al.Facile synthesis of porous carbon nitride spheres with hierarchical three-dimensional mesostructures for CO2capture.Nano Res., 2010, 3(9): 632-642.
[43]	WILKE A, WEBER J.Hierarchical nanoporous melamine resin sponges with tunable porosity-porosity analysis and CO2 adsorption properties.J. Mater. Chem., 2011, 21(14): 5226-5229.
[44]	GUTIERREZ M C, CARRIAZO D, MONTE F D, et al.Deep eutectic solvents as both precursors and structure directing agents in thesynthesis of nitrogen doped hierarchical carbons highly suitable for CO2.capture.Energy Environ. Sci., 2011, 4(11): 3535-3544.
[45]	HAO G P, LI W C, LU A H.Lysine-assisted rapid synthesis of crack-free hierarchical carbon monoliths with ahexagonal array of mesopores.Carbon, 2011, 49(12): 3762-3772.
[46]	HAO G P, LI W C, LU A H. Structurally designed synthesis of mechanically stable poly(benzoxazine-co-resol)-based porous carbon monoliths and their application as high-performance CO2 capture sorbents. J. Am. Chem. Soc., 2011,133(29): 11378-11388.
[47]	ZHU B J, LI K X, GUO Z X, et al.Nitrogen-enriched and hierarchically porous carbon macro-spheres-ideal for large-scale CO2 Capture.J. Mater. Chem. A, 2014, 2(15): 5481-5489.
[48]	WANG J C, SENKOVSKA I, KASKEL S, et al.Imine-linked polymer-derived nitrogen-doped microporous carbons with excellent CO2 capture properties.ACS Appl. Mater. Interfaces, 2013, 5(8): 3160-3167.
[49]	CHEN H C, SUN F G, LONG D H, et al.Nitrogen doping effects on the physical and chemical properties of mesoporous carbon. J. Phys. Chem. C, 2013, 117(16): 8318-8328.
[50]	TITRIRICI M M, WHITE R J, ZHAO L.Nitrogen-doped hydrothermal carbons.Green, 2012, 2(1): 25-40.
[51]	FENG S S, LI W, ZHAO D Y, et al.Synthesis of nitrogen-doped hollow carbon nanospheres for CO2 capture.Chem. Commun., 2014, 50(3): 329-331.
[52]	MA X Y, CAO M H, HU C W, et al.Bifunctional HNO3 catalytic synthesis of N-doped porous carbons for CO2 capture. J. Mater. Chem. A, 2013, 1(3): 913-918.