Efficient CO₂ adsorption and mechanism on nitrogen-doped porous carbons

Abstract

In this work, nitrogen-doped porous carbons (NACs) were fabricated as an adsorbent by urea modification and KOH activation. The CO₂ adsorption mechanism for the NACs was then explored. The NACs are found to present a large specific surface area (1920.72– 3078.99 m²·g⁻¹) and high micropore percentage (61.60%–76.23%). Under a pressure of 1 bar, sample NAC-650-650 shows the highest CO₂ adsorption capacity up to 5.96 and 3.92 mmol·g⁻¹ at 0 and 25 °C, respectively. In addition, the CO₂/N₂ selectivity of NAC-650-650 is 79.93, much higher than the value of 49.77 obtained for the nonnitrogen-doped carbon AC-650-650. The CO₂ adsorption capacity of the NAC-650-650 sample maintains over 97% after ten cycles. Analysis of the results show that the CO₂ capacity of the NACs has a linear correlation (R² = 0.9633) with the cumulative pore volume for a pore size less than 1.02 nm. The presence of nitrogen and oxygen enhances the CO₂/N₂ selectivity, and pyrrole-N and hydroxy groups contribute more to the CO₂ adsorption. In situ Fourier transform infrared spectra analysis indicates that CO₂ is adsorbed onto the NACs as a gas. Furthermore, the physical adsorption mechanism is confirmed by adsorption kinetic models and the isosteric heat, and it is found to be controlled by CO₂ diffusion. The CO₂ adsorption kinetics for NACs at room temperature and in pure CO₂ is in accordance with the pseudo-first-order model and Avramís fractional-order kinetic model.

Graphical abstract

Keywords

porous carbon / CO₂ adsorption / nitrogen-doped / adsorption mechanism / kinetics

References

[1] Jian B H, Shao W W, Yong L, Zong C Z, Xin Y W. Debates on the causes of global warming. Advances in Climate Change Research, 2012, 3(1): 38–44

[2] Oktyabrskiy V P. A new opinion of the greenhouse effect. St. Petersburg Polytechnical University Journal. Physics and Mathematics, 2016, 2(2): 124–126

[3] Akitt J W. Some observations on the greenhouse effect at the Earth’s surface. Spectrochimica Acta. Part A: Molecular and Biomolecular Spectroscopy, 2018, 188: 127–134

[4] Roussanaly S, Vitvarova M, Anantharaman R, Berstad D, Hagen B, Jakobsen J, Novotny V, Skaugen G. Techno-economic comparison of three technologies for precombustion CO₂ capture from a lignite-fired IGCC. Frontiers of Chemical Science and Engineering, 2020, 14(3): 436–452

[5] Cometto C, Kuriki R, Chen L J, Maeda K, Lau T C, Ishitani O, Robert M. A carbon Nitride/Fe quaterpyridine catalytic system for photostimulated CO₂-to-CO conversion with visible light. Journal of the American Chemical Society, 2018, 140(24): 7437–7440

[6] Peng H, Lu J, Wu C X, Yang Z X, Chen H, Song W J, Li P Q, Yin H Z. Co-doped MoS₂ NPs with matched energy band and low overpotential high efficiently convert CO₂ to methanol. Applied Surface Science, 2015, 353: 1003–1012

[7] Wang S M, Guan Y, Lu L, Shi Z, Yan S C, Zou Z G. Effective separation and transfer of carriers into the redox sites on Ta₃N₅/Bi photocatalyst for promoting conversion of CO₂ into CH₄. Applied Catalysis B: Environmental, 2018, 224: 10–16

[8] Ban Y J, Zhao M, Yang W S. Metal-organic framework-based CO₂ capture: from precise material design to high-efficiency membranes. Frontiers of Chemical Science and Engineering, 2020, 14(2): 188–215

[9] Li W, Li S. CO₂ adsorption performance of functionalized metal-organic frameworks of varying topologies by molecular simulations. Chemical Engineering Science, 2018, 189: 65–74

[10] Wang X, Guo Q J, Zhao J, Chen L L. Mixed amine-modified MCM-41 sorbents for CO₂ capture. International Journal of Greenhouse Gas Control, 2015, 37: 90–98

[11] Kongnoo A, Tontisirin S, Worathanakul P, Phalakornkule C. Surface characteristics and CO₂ adsorption capacities of acid-activated zeolite 13X prepared from palm oil mill fly ash. Fuel, 2017, 193: 385–394

[12] Kishor R, Ghoshal A K. Amine-modified mesoporous silica for CO₂ adsorption: the role of structural parameters. Industrial & Engineering Chemistry Research, 2017, 56(20): 6078–6087

[13] Guo X Z, Ding L, Kanamori K, Nakanishi K, Yang H. Functionalization of hierarchically porous silica monoliths with polyethyleneimine (PEI) for CO₂ adsorption. Microporous and Mesoporous Materials, 2017, 245: 51–57

[14] Wang Y X, Hu X D, Hao J, Ma R, Guo Q J, Gao H F, Bai H C. Nitrogen and oxygen codoped porous carbon with superior CO₂ adsorption performance: a combined experimental and DFT calculation study. Industrial & Engineering Chemistry Research, 2019, 58(29): 13390–13400

[15] Hu X, Radosz M, Cychosz K A, Thommes M. CO₂-filling capacity and selectivity of carbon nanopores: synthesis, texture, and pore-size distribution from quenched-solid density functional theory (QSDFT). Environmental Science & Technology, 2011, 45(16): 7068–7074

[16] Mehrvarz E, Ghoreyshi A A, Jahanshahi M. Surface modification of broom sorghum-based activated carbon via functionalization with triethylenetetramine and urea for CO₂ capture enhancement. Frontiers of Chemical Science and Engineering, 2017, 11(2): 252–265

[17] Wang X, Guo Q J. CO₂ adsorption behavior of activated coal char modified with tetraethylenepentamine. Energy & Fuels, 2016, 30(4): 3281–3288

[18] Gao S, Ge L, Rufford T E, Zhu Z H. The preparation of activated carbon discs from tar pitch and coal powder for adsorption of CO₂, CH₄ and N₂. Microporous and Mesoporous Materials, 2017, 238: 19–26

[19] Ge X Y, Wu Z S, Wu Z L, Yan Y J, Cravotto G, Ye B C. Enhanced PAHs adsorption using iron-modified coal-based activated carbon via microwave radiation. Journal of the Taiwan Institute of Chemical Engineers, 2016, 64: 235–243

[20] Wei X H, Wu Z L, Du C F, Wu Z S, Ye B C, Cravotto G. Enhanced adsorption of atrazine on a coal-based activated carbon modified with sodium dodecyl benzene sulfonate under microwave heating. Journal of the Taiwan Institute of Chemical Engineers, 2017, 77: 257–262

[21] Chang G Z, Xie J J, Huang Y Q, Liu H C, Yin X L, Wu C Z. Gasification reactivity and pore structure development: effect of intermittent addition of steam on increasing reactivity of PKS biochar with CO₂. Energy & Fuels, 2017, 31(3): 2887–2895

[22] Wang X J, Yuan B Q, Zhou X, Xia Q B, Li Y W, An D L, Li Z. Novel glucose-based adsorbents (Glc-Cs) with high CO₂ capacity and excellent CO₂/CH₄/N₂ adsorption selectivity. Chemical Engineering Journal, 2017, 327: 51–59

[23] Nowrouzi M, Younesi H, Bahramifar N. Superior CO₂ capture performance on biomass-derived carbon/metal oxides nanocomposites from Persian ironwood by H₃PO₄ activation. Fuel, 2018, 223: 99–114

[24] Tiwari D, Bhunia H, Bajpai P K. Adsorption of CO₂ on KOH activated, N-enriched carbon derived from urea formaldehyde resin: kinetics, isotherm and thermodynamic studies. Applied Surface Science, 2018, 439: 760–771

[25] Liu F Q, Wang L L, Li G H, Li W, Li C Q. Hierarchically structured graphene coupled microporous organic polymers for superior CO₂ capture. ACS Applied Materials & Interfaces, 2017, 9(39): 33997–34004

[26] Chang G Z, Wu W, Shi P C, Ma J J, Guo Q J. A promising composite bimetallic catalyst for producing CH₄-rich syngas from bitumite one-step gasification. Energy Conversion and Management, 2020, 205: 112408

[27] Chen J, Yang J, Hu G S, Hu X, Li Z M, Shen S W, Radosz M, Fan M H. Enhanced CO₂ capture capacity of nitrogen-doped biomass-derived porous carbons. ACS Sustainable Chemistry & Engineering, 2016, 4(3): 1439–1445

[28] Yue L M, Xia Q Z, Wang L W, Wang L L, DaCosta H, Yang J, Hu X. CO₂ adsorption at nitrogen-doped carbons prepared by K₂CO₃ activation of urea-modified coconut shell. Journal of Colloid and Interface Science, 2018, 511: 259–267

[29] Chiang Y C, Juang R S. Surface modifications of carbonaceous materials for carbon dioxide adsorption: a review. Journal of the Taiwan Institute of Chemical Engineers, 2017, 71: 214–234

[30] Peyravi M. Synthesis of nitrogen doped activated carbon/polyaniline material for CO₂ adsorption. Polymers for Advanced Technologies, 2018, 29(1): 319–328

[31] Wang M, Fan X Q, Zhang L X, Liu J H, Wang B Z, Cheng R L, Li M L, Tian J J, Shi J L. Probing the role of O-containing groups in CO₂ adsorption of N-doped porous activated carbon. Nanoscale, 2017, 9(44): 17593–17600

[32] Tian Z H, Huang J J, Zhang X, Shao G L, He Q Y, Cao S K, Yuan S G. Ultra-microporous N-doped carbon from polycondensed framework precursor for CO₂ adsorption. Microporous and Mesoporous Materials, 2018, 257: 19–26

[33] Shao L S, Liu M Q, Huang J H, Liu Y N. CO₂ capture by nitrogen-doped porous carbons derived from nitrogen-containing hyper-cross-linked polymers. Journal of Colloid and Interface Science, 2018, 513: 304–313

[34] Serafin J, Narkiewicz U, Morawski A W, Wróbel R J, Michalkiewicz B. Highly microporous activated carbons from biomass for CO₂ capture and effective micropores at different conditions. Journal of CO₂ Utilization, 2017, 18: 73–79

[35] Singh J, Bhunia H, Basu S. CO₂ adsorption on oxygen enriched porous carbon monoliths: kinetics, isotherm and thermodynamic studies. Journal of Industrial and Engineering Chemistry, 2018, 60: 321–332

[36] Simonin J P. On the comparison of pseudo-first order and pseudo-second order rate laws in the modeling of adsorption kinetics. Chemical Engineering Journal, 2016, 300: 254–263

[37] Tiwari D, Bhunia H, Bajpai P K. Development of chemically activated N-enriched carbon adsorbents from urea-formaldehyde resin for CO₂ adsorption: kinetics, isotherm, and thermodynamics. Journal of Environmental Management, 2018, 218: 579–592

[38] Tiwari D, Goel C, Bhunia H, Bajpai P K. Melamine-formaldehyde derived porous carbons for adsorption of CO₂ capture. Journal of Environmental Management, 2017, 197: 415–427

[39] Liu M Q, Shao L S, Huang J H, Liu Y N. O-containing hyper-cross-linked polymers and porous carbons for CO₂ capture. Microporous and Mesoporous Materials, 2018, 264: 104–111

[40] Rashidi N A, Yusup S. An overview of activated carbons utilization for the post-combustion carbon dioxide capture. Journal of CO₂ Utilization, 2016, 13: 1–16

[41] Parshetti G K, Chowdhury S, Balasubramanian R. Biomass derived low-cost microporous adsorbents for efficient CO₂ capture. Fuel, 2015, 148: 246–254

[42] Alhamed Y A, Rather S U, El-Shazly A H, Zaman S F, Daous M A, Al-Zahrani A A. Preparation of activated carbon from fly ash and its application for CO₂ capture. Korean Journal of Chemical Engineering, 2015, 32(4): 723–730

[43] Liu D D, Gao J H, Cao Q X, Wu S H, Qin Y K. Improvement of activated carbon from Jixi bituminous coal by air preoxidation. Energy & Fuels, 2017, 31(2): 1406–1415

[44] Yue L, Rao L, Wang L, An L, Hou C, Ma C, DaCosta H, Hu X. Efficient CO₂ adsorption on nitrogen-doped porous carbons derived from D-glucose. Energy & Fuels, 2018, 32(6): 6955–6963

[45] Sánchez-Sánchez Á, Suárez-García F, Martínez-Alonso A, Tascón J M D. Influence of porous texture and surface chemistry on the CO₂ adsorption capacity of porous carbons: acidic and basic site interactions. ACS Applied Materials & Interfaces, 2014, 6(23): 21237–21247

[46] Yaumi A L, Bakar M Z A, Hameed B H. Reusable nitrogen-doped mesoporous carbon adsorbent for carbon dioxide adsorption in fixed-bed. Energy, 2017, 138: 776–784

[47] Kudin K N, Ozbas B, Schniepp H C, Prud’Homme R K, Aksay I A, Car R. Raman spectra of graphite oxide and functionalized graphene sheets. Nano Letters, 2008, 8(1): 36–41

[48] Shao L S, Wang S Q, Liu M Q, Huang J H, Liu Y N. Triazine-based hyper-cross-linked polymers derived porous carbons for CO₂ capture. Chemical Engineering Journal, 2018, 339: 509–518

[49] Puthiaraj P, Ahn W S. Facile synthesis of microporous carbonaceous materials derived from a covalent triazine polymer for CO₂ capture. Journal of Energy Chemistry, 2017, 26(5): 965–971

[50] Zhang G J, Zhao P Y, Hao L X, Xu Y. Amine-modified SBA-15(P): a promising adsorbent for CO₂ capture. Journal of CO₂ Utilization, 2018, 24: 22–33

Acknowledgments

This work is funded by the National Key Research and Development Program of China (Grant No. 2018YFB0605401); the National Natural Science Foundation of China (Grant No. 21868025); the National First-rate Discipline Construction Project of Ningxia (No. NXYLXK2017A04); the Key Research and Development Program of Ningxia Province, China (No. 2018BCE01002); and Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (Grant No. 2020-KF-39).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-020-1967-0 and is accessible for authorized users.

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