Study of CO2 adsorption on amine functionalized graphene oxide porous materials

doi:10.11949/j.issn.0438-1157.20190018

Abstract

Abstract:

CO₂ adsorbents were prepared by chemical grafting ethylenediamine(EDA), diethylenetriamine(DETA), tetraethylenepentamime(TEPA), and polyethyleneimine(PEI) onto surface of graphene oxide combined with the ultrasound treatment. The pore diameter of amine functionalized GO is 1.35—4.34 nm, and the surface area is 98.032—210.465 m²/g. Among the four amine functionalized GO, the PEI functionalized GO has the largest CO₂ adsorption capacity, reaching 1.5 mmol/g at 70°C. Besides, the adsorbent also exhibited stable cyclic adsorption-regeneration performance with almost unchanged adsorption capacity after 20 cycles. The type of isothermal adsorption line is type Ⅰ, and the Avrami simulation results agree well with the adsorption experimental data.

Key words: graphene oxide, amine functionalization, adsorption, CO₂ capture, preparation

摘要：

以乙二胺(EDA)、二乙烯三胺(DETA)、四乙烯五胺(TEPA)、聚乙烯亚胺(PEI)等多胺基化合物为表面改性剂，氧化石墨烯(GO)材料为载体，采用嫁接法辅以超声处理制备了表面胺基功能化多孔吸附材料，用于CO₂气体的吸附捕集。所制备的多孔吸附材料孔径约为1.35~4.34 nm，比表面积约为98.032~210.465 m²/g。制备的四种吸附材料中，以PEI功能化吸附材料对CO₂的吸附容量最大，70℃下达到了1.5 mmol/g，且经过20次循环吸附/脱附实验后，其CO₂吸附量基本不变。吸附过程的吸附等温线线型为Ⅰ型优惠型，另外吸附实验数据与Avrami模型模拟结果符合性较好。

关键词: 石墨烯, 胺基功能化, 吸附, 二氧化碳捕集, 制备

CLC Number:

TQ 465.92

Yamin LIU, Lei PENG, Fengying SU, Xiangxiang WANG, Yizhen HUANG, Zaichun LIN, Xiaojing YU, Yishan PEI. Study of CO₂ adsorption on amine functionalized graphene oxide porous materials[J]. CIESC Journal, 2019, 70(5): 2016-2024.

刘亚敏, 彭蕾, 苏凤英, 王湘湘, 黄艺真, 林在春, 喻晓静, 裴义山. 多孔胺基化氧化石墨烯基材料对CO₂的吸附性能研究[J]. 化工学报, 2019, 70(5): 2016-2024.

Figures/Tables 13

Fig.1 Raman spectra of GO

Fig.2 XRD patterns of GO, EDA-GO, DETA-GO, TEPA-GO and PEI-GO

Table 1 Textural properties of GO, EDA-GO, DETA, TEPA-GO and PEI-GO

样品	比表面积/(m²/g)	孔容/(cm³/g)	孔径(BJH)/nm
GO	289.028	0.046	1.91
EDA-GO	98.032	0.016	4.34
DETA-GO	210.465	0.043	1.73
TEPA-GO	194.484	0.042	1.69
PEI-GO	162.042	0.031	1.35

Table 2 Elemental analysis of GO and amine functionalized GO

Sample	C/%(mass)	N/%(mass)	O/%(mass)
GO	62.17	0.08	20.24
EDA-GO	59.37	2.34	18.06
DETA-GO	53.52	4.18	14.84
TEPA-GO	52.68	4.84	14.66
PEI-GO	51.06	5.42	13.08

Fig.3 SEM images of GO, EDA-GO, TEPA-GO and PEI-GO

Fig.4 TGA curves of samples

Fig.5 FTIR spectrums of GO, EDA-GO, DETA-GO and PEI-GO

Table 3 Adsorption capacity of samples

Sample	Adsorption capacity/(mmol CO₂/g)
Sample	30℃	50℃	70℃
PEI-GO	0.3	1.2	1.5
TEPA-GO	0.3	0.9	1.3
DETA-GO	0.3	0.8	1.2
EDA-GO	0.1	0.5	0.7
GO	0.2	0.1	0

Table 4 Constants of Langmuir model for CO2 adsorption on PEI-GO

T/℃	q _m /(mmol/g)	k _L/min^?1	R ²
70	1.8523	0.3737	0.997
50	1.59147	0.2257	0.988
30	0.50101	0.15023	0.979

Fig.6 CO2 adsorption isotherms of PEI-GO at 30℃, 50℃ and 70℃

Fig.7 Avrami models on experimental CO2 uptake of PEI-GO at various adsorption temperatures

Table 5 Constants of Avrami model for CO2 adsorption on PEI-GO

T/℃	q _e/(mmol/g)	k _a/min^-1	n	R ²	q _a/(mmol/g)
30	0.35096	0.46997	1.12044	0.998	0.3
50	1.28668	0.27768	1.28763	0.998	1.2
70	1.61234	0.272	1.05424	0.999	1.5

Fig.8 Recycle adsorption/desorption runs of PEI-GO

References 39

1	Boothandford M E , Abanades J C , Anthony E J , et al . Carbon capture and storage update[J]. Energy & Environmental Science, 2014, 7(1): 130-189.
2	Dowell N M , Fennell P S , Shah N , et al . The role of CO₂ capture and utilization in mitigating climate change[J]. Nature Climate Change, 2017, 7(4): 243-249.
3	Yuan W , Li Z , Alexander O , et al . A review of post-combustion CO₂ capture technologies from coal-fired power plants[J]. Energy Procedia, 2017, 114: 650-665.
4	Mohamed K , Yann L M , Olivier A , et al . Up-to-date CO₂ capture in thermal power plants[J]. Energy Procedia, 2017, 114: 95-103.
5	Chiang Y C , Juang R S . Surface modifications of carbonaceous materials for carbon dioxide adsorption: a review[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 71: 214-234.
6	Sanz-Pérez E S , Dantas T C M , Arencibia A , et al . Reuse and recycling of amine-functionalized silica materials for CO₂ adsorption[J]. Chemical Engineering Journal, 2017, 308: 1021-1033.
7	Creamer A E , Gao B . Carbon-based adsorbents for post-combustion CO₂ capture: a critical review[J]. Environmental Science & Technology, 2016, 50(14): 7276.
8	Kishor R , Ghoshal A K . Amine-modified mesoporous silica for CO₂ adsorption: the role of structural parameters[J]. Industrial & Engineering Chemistry Research, 2017, 56(20): 6078-6087.
9	张文静, 吴烨, 蔡天意, 等 . 胺基CO₂固体吸附剂脱碳特性及SO₂的影响[J]. 化工学报, 2018, 69(4): 1586-1594.
	Zhang W J , Wu Y , Cai T Y , et al . Effect of SO₂ on CO₂ sorption characteristics using solid amine CO₂ sorbent[J]. CIESC Journal, 2018, 69(4): 1586-1594.
10	Chen C , Lee Y R , Ahn W S . CO₂ adsorption over metal-organic frameworks: a mini review[J]. Journal of Nanoscience & Nanotechnology, 2016, 16(5): 4291.
11	陈敏玲, 王兴杰, 肖静, 等 . 淀粉基多孔碳材料的制备及其吸附CO₂/CH₄性能[J]. 化工学报, 2018, 69(1): 455-463.
	Chen M L , Wang X J , Xiao J , et al . Preparation of porous carbon material from starch and its performance for separation of CO₂/CH₄ [J]. CIESC Journal, 2018, 69(1): 455-463.
12	谢丹妍, 邢华斌, 张治国, 等 . 多孔氢键金属-有机框架材料对乙炔和二氧化碳的吸附分离[J]. 化工学报, 2017, 68(1): 154-162.
	Xie D Y , Xing H B , Zhang Z G , et al . Porous hydrogen-bonded organometallic frameworks for adsorption separation of acetylene and carbon dioxide[J]. CIESC Journal, 2017, 68(1): 154-162.
13	Balasubramanian R , Chowdhury S . Recent advances and progress in the development of graphene-based adsorbents for CO₂ capture[J]. J. Mater. Chem. A, 2015, 3(44): 21968-21989.
14	Chisholm M F , Lee J , Guo J , et al . Functionalization of graphene[J]. Microscopy & Microanalysis, 2015, 21(S3): 737-738.
15	Gadipelli S , Zheng X G . Graphene-based materials: synthesis and gas sorption, storage and separation[J]. Progress in Materials Science, 2015, 69(69): 1-60.
16	Balandin A A , Ghosh S , Bao W , et al . Superior thermal conductivity of single-layer graphene[J]. Nano Letters, 2008, 8(3): 902.
17	Ghosh A , Subrahmanyam K S , Krishna K S , et al . Uptake of H₂ and CO₂ by graphene[J]. Journal of Physical Chemistry C, 2008, 112(40): 15704-15707.
18	Mishra A K , Ramaprabhu S . Carbon dioxide adsorption in graphene sheets[J]. AIP Advances, 2011, 1(3): 321.
19	Hong S M , Kim S H , Lee K B . Adsorption of carbon dioxide on 3-aminopropyl-triethoxysilane modified graphite oxide[J]. Energy & Fuels, 2013, 27(6): 3358-3363.
20	Sui Z Y , Cui Y , Zhu J H , et al . Preparation of three-dimensional graphene oxide-polyethylenimine porous materials as dye and gas adsorbents [J]. ACS Applied Materials & Interfaces, 2013, 5(18): 9172.
21	Chowdhury S , Parshetti G K , Balasubramanian R . Post-combustion CO₂ capture using mesoporous TiO₂ /graphene oxide nanocomposites[J]. Chemical Engineering Journal, 2015, 263: 374-384.
22	Marcano D C , Kosynkin D V , Berlin J M , et al . Improved synthesis of graphene oxide [J]. ACS Nano, 2010, 4 (8): 4806-4814.
23	Ferrari A C , Basko D M . Raman spectroscopy as a versatile tool for studying the properties of graphene[J]. Nature Nanotechnology, 2013, 8(4): 235-246.
24	Ling X , Zhang J . Interference phenomenon in graphene-enhanced Raman scattering[J]. Journal of Physical Chemistry C, 2011, 115(6): 2835-2840.
25	Gupta A , Chen G , Joshi P , et al . Raman scattering from high-frequency phonons in supported n-graphene layer films[J]. Nano Letters, 2006, 6(12): 2667-2673.
26	Graf D , Molitor F , Ensslin K , et al . Spatially resolved Raman spectroscopy of single- and few-layer graphene[J]. Nano Letters, 2006, 7(2): 238.
27	Liu J , Jeong H , Liu J , et al . Reduction of functionalized graphite oxides by trioctylphosphine in non-polar organic solvents[J]. Carbon, 2010, 48(8): 2282-2289.
28	Kumar A S K , Rajesh N . Exploring the interesting interaction between graphene oxide, Aliquat-336 (a room temperature ionic liquid) and chromium(Ⅵ) for wastewater treatment[J]. RSC Advances, 2013, 3(8): 2697-2709.
29	Fan L , Luo C , Li X , et al . Fabrication of novel magnetic chitosan grafted with graphene oxide to enhance adsorption properties for methyl blue[J]. Journal of Hazardous Materials, 2012, S215/S216(10): 272-279.
30	Zhao Y , Ding H , Zhong Q . Preparation and characterization of aminated graphite oxide for CO₂ capture[J]. Applied Surface Science, 2012, 258(10): 4301-4307.
31	尚玉, 张东, 刘艳云, 等 . 电化学还原法制备石墨烯:制备与表征[J]. 功能材料, 2015, 46(16): 16009-16015.
	Shang Y , Zhang D , Liu Y Y , et al . Synthesis of graphene via electrochemical reduction method: preparation and characterization [J]. Journal of Functional Materials, 2015, 46(16): 16009-16015.
32	叶振华 . 化工吸附分离过程[M]. 北京: 中国石化出版社, 1992: 41
	Ye Z H . Chemical Engineering Adsorption Processes[M]. Beijing: China Petrochemical Press, 1992: 41
33	Ho Y S . Citation review of Lagergren kinetic rate equation on adsorption reactions[J]. Scientometrics, 2004, 59: 171-177.
34	Ho Y S . Review of second-order models for adsorption systems[J]. J. Hazard. Mater., 2006,136: 681-689.
35	Plazinski W , Rudzinski W , Plazinska A . Theoretical models of sorption kinetics including a surface reaction mechanism: a review[J]. Adv. Colloid. Interface. Sci., 2009, 152(1/2): 2-13.
36	Serna-Guerrero R , Sayari A . Modeling adsorption of CO₂ on amine-functionalized mesoporous silica(Ⅱ): Kinetics and breakthrough curves[J]. Chem. Eng. J., 2010, 161(1/2): 182-190.
37	Avrami M . Kinetics of phase change(Ⅰ): General theory[J]. Journal of Chemical Physics, 1939, 7(12): 1103-1112.
38	Avrami M . Granulation, phase change, and microstructure kinetics of phase change(Ⅲ)[J]. Journal of Chemical Physics, 1941, 9(2): 177-184.
39	Benedict J B , Coppens P . Kinetics of the single-crystal to single-crystal two-photon photodimerization of alpha-trans-cinnamic acid to alpha-truxillic acid[J]. Journal of Physical Chemistry A, 2009, 113(13): 3116-3120.

[1]	Bingchun SHENG, Jianguo YU, Sen LIN. Study on lithium resource separation from underground brine with high concentration of sodium by aluminum-based lithium adsorbent [J]. CIESC Journal, 2023, 74(8): 3375-3385.
[2]	Ruihang ZHANG, Pan CAO, Feng YANG, Kun LI, Peng XIAO, Chun DENG, Bei LIU, Changyu SUN, Guangjin CHEN. Analysis of key parameters affecting product purity of natural gas ethane recovery process via ZIF-8 nanofluid [J]. CIESC Journal, 2023, 74(8): 3386-3393.
[3]	Yan GAO, Peng WU, Chao SHANG, Zejun HU, Xiaodong CHEN. Preparation of magnetic agarose microspheres based on a two-fluid nozzle and their protein adsorption properties [J]. CIESC Journal, 2023, 74(8): 3457-3471.
[4]	Ji CHEN, Ze HONG, Zhao LEI, Qiang LING, Zhigang ZHAO, Chenhui PENG, Ping CUI. Study on coke dissolution loss reaction and its mechanism based on molecular dynamics simulations [J]. CIESC Journal, 2023, 74(7): 2935-2946.
[5]	Wentao WU, Liangyong CHU, Lingjie ZHANG, Weimin TAN, Liming SHEN, Ningzhong BAO. High-efficient preparation of cardanol-based self-healing microcapsules [J]. CIESC Journal, 2023, 74(7): 3103-3115.
[6]	Zhilong WANG, Ye YANG, Zhenzhen ZHAO, Tao TIAN, Tong ZHAO, Yahui CUI. Influence of mixing time and sequence on the dispersion properties of the cathode slurry of lithium-ion battery [J]. CIESC Journal, 2023, 74(7): 3127-3138.
[7]	Jiali GE, Tuxiang GUAN, Xinmin QIU, Jian WU, Liming SHEN, Ningzhong BAO. Synthesis of FeF₃ nanoparticles covered by vertical porous carbon for high performance Li-ion battery cathode [J]. CIESC Journal, 2023, 74(7): 3058-3067.
[8]	Jie WANG, Xiaolin QIU, Ye ZHAO, Xinyang LIU, Zhongqiang HAN, Yong XU, Wenhan JIANG. Preparation and properties of polyelectrolyte electrostatic deposition modified PHBV antioxidant films [J]. CIESC Journal, 2023, 74(7): 3068-3078.
[9]	Feng ZHU, Kailin CHEN, Xiaofeng HUANG, Yinzhu BAO, Wenbin LI, Jiaxin LIU, Weiqiang WU, Wangwei GAO. Performance study of KOH modified carbide slag for removal of carbonyl sulfide [J]. CIESC Journal, 2023, 74(6): 2668-2679.
[10]	Lei MAO, Guanzhang LIU, Hang YUAN, Guangya ZHANG. Efficient preparation of carbon anhydrase nanoparticles capable of capturing CO₂ and their characteristics [J]. CIESC Journal, 2023, 74(6): 2589-2598.
[11]	Caihong LIN, Li WANG, Yu WU, Peng LIU, Jiangfeng YANG, Jinping LI. Effect of alkali cations in zeolites on adsorption and separation of CO₂/N₂O [J]. CIESC Journal, 2023, 74(5): 2013-2021.
[12]	Chenxin LI, Yanqiu PAN, Liu HE, Yabin NIU, Lu YU. Carbon membrane model based on carbon microcrystal structure and its gas separation simulation [J]. CIESC Journal, 2023, 74(5): 2057-2066.
[13]	Shaoyun CHEN, Dong XU, Long CHEN, Yu ZHANG, Yuanfang ZHANG, Qingliang YOU, Chenglong HU, Jian CHEN. Preparation and adsorption properties of monolayer polyaniline microsphere arrays [J]. CIESC Journal, 2023, 74(5): 2228-2238.
[14]	Hao WANG, Siyang TANG, Shan ZHONG, Bin LIANG. An investigation of the enhancing effect of solid particle surface on the CO₂ desorption behavior in chemical sorption process with MEA solution [J]. CIESC Journal, 2023, 74(4): 1539-1548.
[15]	Yu PAN, Zihang WANG, Jiayun WANG, Ruzhu WANG, Hua ZHANG. Heat and moisture performance study of Cur-LiCl coated heat exchanger [J]. CIESC Journal, 2023, 74(3): 1352-1359.

Study of CO₂ adsorption on amine functionalized graphene oxide porous materials

多孔胺基化氧化石墨烯基材料对CO₂的吸附性能研究

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 13

References 39

Related Articles 15

Recommended Articles

Metrics

Comments