Abstract
Carbon materials have attracted great attention in CO2 capture and energy storage due to their excellent characteristics such as tunable pore structure, modulated surface properties and superior bulk conductivities, etc. Biomass, provided by nature with non-toxic, widespread, abundant, and sustainable advantages, is considered to be a very promising precursor of carbons for the view of economic, environmental, and societal issues. However, the preparation of high-performance biomass-derived carbons is still a big challenge because of the multistep process for their synthesis and subsequent activation. Herein, hierarchically porous structured carbon materials have been prepared by directly carbonizing dried cauliflowers without any addition of agents and activation process, featuring with large specific surface area, hierarchically porous structure and improved pore volume, as well as suitable nitrogen content. Being used as a solid-state CO2 adsorbent, the obtained product exhibited a high CO2 adsorption capacity of 3.1 mmol g−1 under 1 bar and 25 °C and a remarkable reusability of 96.7% retention after 20 adsorption/regeneration cycles. Our study reveals that choosing a good biomass source was significant as the unique structure of precursor endows the carbonized product with abundant pores without the need of any post-treatment. Used as an electrode material in electrochemical capacitor, the non-activated porous carbon displayed a fairly high specific capacitance of 228.9 F g−1 at 0.5 A g−1 and an outstanding stability of 99.2% retention after 5000 cycles at 5 A g−1.
Hierarchically porous structured carbon materials are prepared by directly carbonizing dried cauliflower without any agents and process of activation for high performance of CO2 capture and capacitor.
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References
Biniak S, Pakuła M, Świątkowski A, Bystrzejewski M, Błażewicz S (2010) Influence of high-temperature treatment of granular activated carbon on its structure and electrochemical behavior in aqueous electrolyte solution. J Mater Res 25:1617–1628. https://doi.org/10.1557/JMR.2010.0207
Caturla F, Molina-Sabio M, Rodriguez-Reinoso F (1991) Preparation of activated carbon by chemical actication with ZnCl2. Carbon 29:999–1007. https://doi.org/10.1016/0008-6223(91)90179-M
Cheng P, Gao S, Zang P, Yang X, Bai Y, Xu H, Liu Z, Lei Z (2015) Hierarchically porous carbon by activation of shiitake mushroom for capacitive energy storage. Carbon 93:315–324. https://doi.org/10.1016/j.carbon.2015.05.056
Cheng P, Li T, Yu H, Zhi L, Liu ZH, Lei Z (2016) Biomass-derived carbon fiber aerogel as binder free electrode for high-rate supercapacitor. J Phys Chem C 120:2079–2086. https://doi.org/10.1021/acs.jpcc.5b11280
Choi SH, Kim DH, Raghu AV, Reddy KR, Lee H, Yoon KS, Jeong HM, Kim BK (2012) Properties of graphene/waterborne polyurethane nanocomposites cast from colloidal dispersion mixtures. J. Macromol. Sci Part B: Phys 51:197–207. https://doi.org/10.1080/00222348.2011.583193
Dawson R, Cooper AI, Adams DJ (2013) Chemical functionalization strategies for carbon dioxide capture in microporous organic polymers. Polym Int 62:345–352. https://doi.org/10.1002/pi.4407
Deng J, Li M, Wang Y (2016) Biomass-derived carbon: synthesis and application on energy storage and conversion. Green Chem 18:4824–4854. https://doi.org/10.1039/C6GC01172A
Ding B, Yuan CZ, Shen LF, Xu GY, Nie P, Zhang XG (2013) Encapsulating sulfur into hierarchically ordered porous carbon as a high-performance cathode for lithium–sulfur batteries. Chem Eur J 19:1013–1019. https://doi.org/10.1002/chem.201202127
Elmouwahidi A, Zapata-Benabithe Z, Carrasco-Marín F, Moreno-Castilla C (2012) Activated carbons from KOH-activation of argan (Argania spinosa) seed shells as supercapacitor electrodes. Bioresor Technol 111:185–192. https://doi.org/10.1016/j.biortech.2012.02.010
Ferrer ML, Gutierrez MC, Carriazo D, Patiño J, Lopez-Salas N (2016) Phosphorus-doped carbon–carbon nanotube hierarchical monoliths as true three-dimensional electrodes in supercapacitor cells. J Mater Chem A 4:1251–1263. https://doi.org/10.1039/C5TA09210H
Frackowiak E, Delpeux S, Jurewicz K, Szostak K, Cazorla-Amoros D, Beguin F (2002) Enhanced capacitance of carbon nanotubes through chemical activation. Chem Phys Lett 361:35–41. https://doi.org/10.1016/S0009-2614(02)00684-X
Gong J, Lin H, Antonietti M, Yuan J (2016) Nitrogen-doped porous carbon nanosheets derived from poly(ionic liquid): hierarchical pore structures for efficient CO2 capture and dye removal. J Mater Chem A 4:7313–7321. https://doi.org/10.1039/C6TA01945E
Hao W, Björkman E, Lilliestråle M, Hedin N (2013) Activated carbons prepared from hydrothermally carbonized waste biomass used as adsorbents for CO2. Appl Energy 112:526–532. https://doi.org/10.1016/j.apenergy.2013.02.028
Hao P, Zhao Z, Tian J, Li H, Sang Y, Yu G, Cai H, Liu H, Wong CP, Umar A (2014) Hierarchical porous carbon aerogel derived from bagasse for high performance supercapacitor electrode. Nano 6:12120–12129. https://doi.org/10.1039/C4NR03574G
Hassan M, Reddy KR, Haque E, Minett AI, Gomes VG (2013) High-yield aqueous phase exfoliation of graphene for facile nanocomposite synthesis via emulsion polymerization. J Colloid and Interface Sci 410:43–51. https://doi.org/10.1016/j.jcis.2013.08.006
He X, Ling P, Qiu J, Yu M, Zhang X, Yu C, Zheng M (2013) Efficient preparation of biomass-based mesoporous carbons for supercapacitors with both high energy density and high power density. J Power Sources 240:109–113. https://doi.org/10.1016/j.jpowsour.2013.03.174
Hu S, Zhang S, Pan N, Hsieh YL (2014) High energy density supercapacitors from lignin derived submicron activated carbon fibers in aqueous electrolytes. J Power Sources 270:106–112. https://doi.org/10.1016/j.jpowsour.2014.07.063
Karthikeyan K, Amaresh S, Lee SN, Sun X, Aravindan V, Lee YG, Lee YS (2014) Construction of high-energy-density supercapacitors from pine-cone-derived high-surface-area carbons. ChemSusChem 7:1435–1442. https://doi.org/10.1002/cssc.201301262
Khan MU, Reddy KR, Snguanwongchai T, Haque E, Gomes VG (2016) Polymer brush synthesis on surface modified carbon nanotubes via in situ emulsion polymerization. Colloid and Polymer Sci 294:1599–1610. https://doi.org/10.1007/s00396-016-3922
Kim TY, Jung G, Yoo S, Suh KS, Ruoff RS (2013) Activated graphene-based carbons as supercapacitor electrodes with macro- and mesopores. ACS Nano 7:6899–6905. https://doi.org/10.1021/nn402077v
Li Z, Xu Z, Tan X, Wang H, Holt CMB, Stephenson T, Olsen BC, Mitlin D (2013) Mesoporous nitrogen-rich carbons derived from protein for ultra-high capacity battery anodes and supercapacitors. Energy Environ Sci 6:871–878. https://doi.org/10.1039/C2EE23599D
Li ZJ, Lv W, Zhang C, Li BH, Kang FY, Yang QHA (2015) Sheet-like porous carbon for high-rate supercapacitors produced by the carbonization of an eggplant. Carbon 92:11–14. https://doi.org/10.1016/j.carbon.2015.02.054
Li B, Dai F, Xiao Q, Yang L, Shen J, Zhang C, Cai M (2016a) Activated carbon from biomass transfer for high-energy density lithium-ion supercapacitors. Adv Energy Mater 6. https://doi.org/10.1002/aenm.201600802
Li Y, Wang G, Wei T, Fan Z, Yan P (2016b) Nitrogen and sulfur co-doped porous carbon nanosheets derived from willow catkin for supercapacitors. Nano Energy 19:165–175. https://doi.org/10.1016/j.nanoen.2015.10.038
Liang T, Chen C, Li X, Zhang J (2016) Popcorn-derived porous carbon for energy storage and CO2 capture. Langmuir 32:8042–8049. https://doi.org/10.1021/acs.langmuir.6b01953
Long C, Chen X, Jiang L, Zhi L, Fan Z (2015) Porous layer-stacking carbon derived from in-built template in biomass for high volumetric performance supercapacitors. Nano Energy 12:141–151. https://doi.org/10.1016/j.nanoen.2014.12.014
Ma G, Yang Q, Sun K, Peng H, Ran F, Zhao X, Lei Z (2015) Nitrogen-doped porous carbon derived from biomass waste for high-performance supercapacitor. Bioresor Technol 197:137–142. https://doi.org/10.1016/j.biortech.2015.07.100
Min YL, He GQ, Xu QJ, Chen YC (2014) Dual-functional MoS2 sheet-modified CdS branchlike heterostructures with enhanced photostability and photocatalytic activity. J Mater Chem A 2:2578–2584. https://doi.org/10.1039/C3TA14240J
Olivares-Marin M, Fernandez JA, Lazaro MJ, Fernandez-Gonzalez C, Macias-Garcia A, Gomez-Serrano V, Stoeckli F, Centeno TA (2009) Cherry stones as precursor of activated carbons for supercapacitors. Mater Chem Phys 114:323–327. https://doi.org/10.1016/j.matchemphys.2008.09.010
Peng C, Yan XB, Wang RT, Lang JW, Oub YJ, Xue QJ (2013) Promising activated carbons derived from waste tea-leaves and their application in high performance supercapacitors electrodes. Electrochim Acta 87:401–408. https://doi.org/10.1016/j.electacta.2012.09.082
Peng C, Lang J, Xu S, Wang X (2014) Oxygen-enriched activated carbons from pomelo peel in high energy density supercapacitor. RSC Adv 4:54662–54667. https://doi.org/10.1039/C4RA09395J
Pesticide AA, Sheikh SA (2013) Assessment of pesticide residues in cauliflower through gas chromatography–μECD and high performance liquid chromatography (HPLC) analysis. Int J Agric Sci Res (IJASR) 3:7–16
Plaza MG, González AS, Pevida C, Pis JJ, Rubiera F (2012) Valorisation of spent coffee grounds as CO2 adsorbents for postcombustion capture applications. Appl Energy 99:272–279. https://doi.org/10.1016/j.apenergy.2012.05.028
Prodhan MDH, Papadakis EN, Mourkidou EP (2016) Variability of pesticide residues in cauliflower units collected from a field trial and market places in Greece. J Environ Sci Health B 56:644–653. https://doi.org/10.1080/03601234.2016.1181922
Qiao Z, Chen M, Wang C, Yuan Y (2014) Humic acids-based hierarchical porous carbons as high-rate performance electrodes for symmetric supercapacitors. Bioresor Technol 163:386–389. https://doi.org/10.1016/j.biortech.2014.04.095
Qie L, Chen W, Xu H, Xiong X, Jiang Y, Zou F, Hu X, Xin Y, Zhang Z, Huang Y (2013) Synthesis of functionalized 3D hierarchical porous carbon for high-performance supercapacitors. Energy Environ Sci 6:2497–2504. https://doi.org/10.1039/C3EE41638K
Qu J, Geng C, Lv S, Shao G, Ma S, Wu M (2015) Nitrogen, oxygen and phosphorus decorated porous carbons derived from shrimp shells for supercapacitors. Electrochim Acta 176:982–988. https://doi.org/10.1016/j.electacta.2015.07.094
Reddy KR, Sin BC, Yoo CH, Park W, Ryu KS, Lee JS, Sohnc D, Lee Y (2008) A new one-step synthesis method for coating multi-walled carbon nanotubes with cuprous oxide nanoparticles. Scr Mater 58:1010–1013. https://doi.org/10.1016/j.scriptamat.2008.01.047
Reddy KR, Sin BC, Yoo CH, Sohn D, Lee Y (2009a) Coating of multiwalled carbon nanotubes with polymer nanospheres through microemulsion polymerization. J Colloid and Interface Sci 340:160–165. https://doi.org/10.1016/j.jcis.2009.08.044
Reddy KR, Sin BC, Ryu KS, Noh J, Lee Y (2009b) In situ self-organization of carbon black–polyaniline composites from nanospheres to nanorods: synthesis, morphology, structure and electrical conductivity. Synth Met 159:1934–1939. https://doi.org/10.1016/j.synthmet.2009.06.018
Reddy KR, Jeong HM, Lee Y, Raghu AV (2010) Synthesis of MWCNTs-core/thiophene polymer-sheath composite nanocables by a cationic surfactant-assisted chemical oxidative polymerization and their structural properties. J Polym Sci Part A 48:1477–1484. https://doi.org/10.1002/pola.23883
Reddy KR, Gomes VG, Hassan M (2014) Carbon functionalized TiO2 nanofibers for high efficiency photocatalysis. Mater Res Exp 1:015012
Reddy KR, Hassan M, Gomes VG (2015) Hybrid nanostructures based on titanium dioxide for enhanced photocatalysis. Appl Catal A Gen 489:1–16. https://doi.org/10.1016/j.apcata.2014.10.001
Rinaldi A, Zhang J, Frank B, Su DS, Abd Hamid SB, Schlögl R (2010) Oxidative purification of carbon nanotubes and its impact on catalytic performance in oxidative dehydrogenation reactions. ChemSusChem 3:254–260. https://doi.org/10.1002/cssc.200900179
Rufford TE, Hulicova-Jurcakova D, Khosla K, Zhu Z, Lu GQ (2010) Microstructure and electrochemical double-layer capacitance of carbon electrodes prepared by zinc chloride activation of sugar cane bagasse. J Power Sources 195:912–918. https://doi.org/10.1016/j.jpowsour.2009.08.048
Sun L, Tian C, Li M, Meng X, Wang L, Wang R, Yin J, Fu H (2013) From coconut shell to porous graphene-like nanosheets for high-power supercapacitors. J Mater Chem A 1:6462–6470. https://doi.org/10.1039/C3TA10897J
Sun L, Tian C, Fu Y, Yang Y, Yin J, Wang L, Fu H (2014) Nitrogen-doped porous graphitic carbon as an excellent electrode material for advanced supercapacitors. Chem Eur J 20:564–574. https://doi.org/10.1002/chem.201303345
Taer E, Deraman M, Talib IA (2011) Preparation of a highly porous binderless activated carbon monolith from rubber wood sawdust by a multi-step activation process for application in supercapacitors. Int J Electrochem Sci 6:3301–3315
Tai Z, Yan X, Lang J, Xue Q (2012) Enhancement of capacitance performance of flexible carbon nanofiber paper by adding graphene nanosheets. J Power Sources 199:373–378. https://doi.org/10.1016/j.jpowsour.2011.10.009
Wang HJ, Huang B, Shi XZ, Darilek JL, Yu DS, Sun WX, Zhao YC, Chang Q, Öborn I (2008) Major nutrient balances in small-scale vegetable farming systems in peri-urban areas in China. Nutr Cycl Agroecosyst 81:203–218. https://doi.org/10.1007/s10705-007-9157-8
Wang L, Mu G, Tian C, Sun L, Zhou W, Yu P, Yin J, Fu H (2013) Porous graphitic carbon nanosheets derived from cornstalk biomass for advanced supercapacitors. ChemSusChem 6:660–669. https://doi.org/10.1002/cssc.201200990
Wang L, Zheng Y, Zhang Q, Zuo L, Chen S, Chen S, Hou H, Song Y (2014) Template-free synthesis of hierarchical porous carbon derived from low-cost biomass for high-performance supercapacitors. RSC Adv 4:51072–51079. https://doi.org/10.1039/C4RA07955H
Wang C, Li Y, He X, Ding Y, Peng Q, Zhao W, Shi E, Wu S, Cao A (2015) Cotton-derived bulk and fiber aerogels grafted with nitrogen-doped graphene. Nano 7:7550–7558. https://doi.org/10.1039/C5NR00996K
Wickramaratne NP, Jaroniec M (2013) Importance of small micropores in CO2 capture by phenolic resin-based activated carbon spheres. J Mater Chem A 1:112–116. https://doi.org/10.1039/C2TA00388K
Wu ZY, Li C, Liang HW, Chen JF, Yu SH (2013) Ultralight, flexible, and fire-resistant carbon nanofiber aerogels from bacterial cellulose. Angew Chem Int Ed 52:2925–2929. https://doi.org/10.1002/ange.201209676
Xu Z, Cai D, Hu Z, Gan L (2014) A combination of porous and crystalline characters in carbon aerogels by a synergistic graphitization. Microporous Mesoporous Mater 195:36–42. https://doi.org/10.1016/j.micromeso.2014.04.013
Xu GY, Han JP, Ding B, Nie P, Pan J, Dou H, Li H, Zhang X (2015) Biomass-derived porous carbon materials with sulfur and nitrogen dual-doping for energy storage. Green Chem 17:1668–1674. https://doi.org/10.1039/C4GC02185A
Yu X, Feng Y, Guan B, Lou XW, Paik U (2016) Carbon coated porous nickel phosphides nanoplates for highly efficient oxygen evolution reaction. Energy Environ Sci 9:1246–1250. https://doi.org/10.1039/C6EE00100A
Zhao A, Samanta A, Sarkar P, Gupta R (2013) Carbon dioxide adsorption on amine-impregnated mesoporous SBA-15 sorbents: experimental and kinetics study. Ind Eng Chem Res 52:6480–6491. https://doi.org/10.1021/ie3030533
Zhou L, Cao H, Zhu S, Hou L, Yuan C (2015) Hierarchical micro-/mesoporous N- and O-enriched carbon derived from disposable cashmere: a competitive cost-effective material for high-performance electrochemical capacitors. Green Chem 17:2373–2382. https://doi.org/10.1039/C4GC02032D
Zhu H, Wang X, Yang F, Yang X (2011) Promising carbons for supercapacitors derived from fungi. Adv Mater 23:2745–2748. https://doi.org/10.1002/adma.201100901
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (21676070), Hebei Natural Science Foundation (B2015208109), Hebei Training Program for Talent Project (A201500117), Five Platform Open Fund Projects of Hebei University of Science and Technology (2015PT37), Hebei One Hundred-Excellent Innovative Talent Program (III) (SLRC2017034), Hebei Science and Technology Project (17214304D, 16214510D), Science Technology Department of Zhejiang Province (2015C31118), Zhejiang Provincial Natural Science Foundation of China (LR16B030001), and International Science and Technology Cooperation Program of Ningbo City (2014D10004).
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Du, J., Yu, Y., Lv, H. et al. Cauliflower-derived porous carbon without activation for electrochemical capacitor and CO2 capture applications. J Nanopart Res 20, 15 (2018). https://doi.org/10.1007/s11051-017-4109-y
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DOI: https://doi.org/10.1007/s11051-017-4109-y