From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture
Graphene-based materials have increasingly attracted attention in recent years. It is a material is recognized worldwide due to its numerous applications in several sectors. However, graphene production involves several challenges: scalability, high costs, and high-quality production. This study syn...
- Autores:
-
Sebem da Silva, Caroline Maria
Oliveira, Marcos
Manera, Christian
Godinho, Marcelo
Perondi, Daniele
Ahmad, Naushad
Nawaz, Asad
Dotto, Guilherme Luiz
Silva, Luis
- Tipo de recurso:
- Article of investigation
- Fecha de publicación:
- 2023
- Institución:
- Corporación Universidad de la Costa
- Repositorio:
- REDICUC - Repositorio CUC
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.cuc.edu.co:11323/14075
- Acceso en línea:
- https://hdl.handle.net/11323/14075
https://repositorio.cuc.edu.co/
- Palabra clave:
- Carbon dioxide
Chars
Grape bagasse
Graphene-like porous carbon nanosheets
Pyrolysis
- Rights
- closedAccess
- License
- Atribución 4.0 Internacional (CC BY 4.0)
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From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture |
| title |
From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture |
| spellingShingle |
From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture Carbon dioxide Chars Grape bagasse Graphene-like porous carbon nanosheets Pyrolysis |
| title_short |
From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture |
| title_full |
From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture |
| title_fullStr |
From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture |
| title_full_unstemmed |
From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture |
| title_sort |
From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture |
| dc.creator.fl_str_mv |
Sebem da Silva, Caroline Maria Oliveira, Marcos Manera, Christian Godinho, Marcelo Perondi, Daniele Ahmad, Naushad Nawaz, Asad Dotto, Guilherme Luiz Silva, Luis |
| dc.contributor.author.none.fl_str_mv |
Sebem da Silva, Caroline Maria Oliveira, Marcos Manera, Christian Godinho, Marcelo Perondi, Daniele Ahmad, Naushad Nawaz, Asad Dotto, Guilherme Luiz Silva, Luis |
| dc.subject.proposal.eng.fl_str_mv |
Carbon dioxide Chars Grape bagasse Graphene-like porous carbon nanosheets Pyrolysis |
| topic |
Carbon dioxide Chars Grape bagasse Graphene-like porous carbon nanosheets Pyrolysis |
| description |
Graphene-based materials have increasingly attracted attention in recent years. It is a material is recognized worldwide due to its numerous applications in several sectors. However, graphene production involves several challenges: scalability, high costs, and high-quality production. This study synthesized graphene-like porous carbon nanosheets (GPCNs) through a thermochemical process under a nitrogen atmosphere using grape bagasse as a precursor. Three temperatures (700, 800, and 900 ºC) of the pyrolysis process were studied. Chemical graphitization and activation were used to form high-specific surface area materials: FeCl3.6H2O(aq) and ZnCl2(s) in a simultaneous activation-graphitization (SAG) method. The materials obtained (GPCN700, GPCN800, and GPCN900) were compared to previously produced chars (C700, C800, and C900). A high specific surface area and total pore volume were obtained for GPCN materials, and GPCN900 presented the highest values: 1062.7 m2g−1 and 0.635 cm3 g−1, respectively. The GPCN and char materials were classified as mesoporous and applied as adsorbents for CO2(g). The GPCN800 presented the best CO2(g) adsorbent, with a CO2(g) adsorption capacity of 168.71 mg g−1. |
| publishDate |
2023 |
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2023-11 |
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2025-04-04T14:53:59Z |
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2025-04-04T14:53:59Z |
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Artículo de revista |
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da Silva, C.M.S., Oliveira, M.L.S., Manera, C. et al. From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture. Environ Sci Pollut Res 30, 113481–113493 (2023). https://doi.org/10.1007/s11356-023-30427-6 |
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0944-1344 |
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https://hdl.handle.net/11323/14075 |
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10.1007/s11356-023-30427-6 |
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1614-7499 |
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Corporación Universidad de la Costa |
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REDICUC - Repositorio CUC |
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da Silva, C.M.S., Oliveira, M.L.S., Manera, C. et al. From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture. Environ Sci Pollut Res 30, 113481–113493 (2023). https://doi.org/10.1007/s11356-023-30427-6 0944-1344 10.1007/s11356-023-30427-6 1614-7499 Corporación Universidad de la Costa REDICUC - Repositorio CUC |
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eng |
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Environmental Science and Pollution Research |
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Acevedo S, Giraldo L, Moreno-Piraján JC (2020) Adsorption of CO2 on Activated Carbons Prepared by Chemical Activation with Cupric Nitrate. ACS Omega 5:10423–10432. https://doi.org/10.1021/acsomega.0c00342 Aïssa B, Memon NK, Ali A, Khraisheh MK (2015) Recent progress in the growth and applications of graphene as a smart material: A review. Front Mater 2:1–19. https://doi.org/10.3389/fmats.2015.00058 Faruque MA Al, Syduzzaman M, Sarkar J, et al (2021) A review on the production methods and applications of graphene-based materials. Nanomaterials 11. https://doi.org/10.3390/nano11092414 Alcaraz L, López Fernández A, García-Díaz I, López FA (2018) Preparation and characterization of activated carbons from winemaking wastes and their adsorption of methylene blue. Adsorpt Sci Technol 36:1331–1351. https://doi.org/10.1177/0263617418770295 Anderson TR, Hawkins E, Jones PD (2016) CO2, the greenhouse effect and global warming: from the pioneering work of Arrhenius and Callendar to today’s Earth System Models. Endeavour 40:178–187. https://doi.org/10.1016/j.endeavour.2016.07.002 Ban CL, Xu Z, Wang D et al (2019) Porous Layered Carbon with Interconnected Pore Structure Derived from Reed Membranes for Supercapacitors. ACS Sustain Chem Eng 7:10742–10750. https://doi.org/10.1021/acssuschemeng.9b01429 Benedetti V, Cordioli E, Patuzzi F, Baratieri M (2019) CO2 Adsorption study on pure and chemically activated chars derived from commercial biomass gasifiers. J CO2 Util 33:46–54. https://doi.org/10.1016/j.jcou.2019.05.008 Benvenuti J, Fisch A, Dos Santos JHZ, Gutterres M (2019) Silica-based adsorbent material with grape bagasse encapsulated by the sol-gel method for the adsorption of Basic Blue 41 dye. J Environ Chem Eng 7:103342. https://doi.org/10.1016/j.jece.2019.103342 Beres C, Costa GNS, Cabezudo I et al (2017) Towards integral utilization of grape pomace from winemaking process: A review. Waste Manag 68:581–594. https://doi.org/10.1016/j.wasman.2017.07.017 Bhagiyalakshmi M, Lee JY, Jang HT (2010) Synthesis of mesoporous magnesium oxide: Its application to CO2 chemisorption. Int J Greenh Gas Control 4:51–56. https://doi.org/10.1016/j.ijggc.2009.08.001 Boningari T, Inturi SNR, Manousiouthakis VI, Smirniotis PG (2018) Facile Synthesis of Flame Spray Pyrolysis-Derived Magnesium Oxide Nanoparticles for CO2 Sorption: Effect of Precursors, Morphology, and Structural Properties. Ind Eng Chem Res 57:9054–9061. https://doi.org/10.1021/acs.iecr.8b00188 Brisebois PP, Siaj M (2020) Harvesting graphene oxide-years 1859 to 2019: A review of its structure, synthesis, properties and exfoliation. J Mater Chem C 8:1517–1547. https://doi.org/10.1039/c9tc03251g Candu N, Man I, Simion A et al (2019) Nitrogen-doped graphene as metal free basic catalyst for coupling reactions. J Catal 376:238–247. https://doi.org/10.1016/j.jcat.2019.07.011 Chang B, Yin H, Zhang X et al (2017) Chemical blowing strategy synthesis of nitrogen-rich porous graphitized carbon nanosheets: Morphology, pore structure and supercapacitor application. Chem Eng J 312:191–203. https://doi.org/10.1016/j.cej.2016.11.129 Cheng J, Hu SC, Sun GT et al (2021) The effect of pyrolysis temperature on the characteristics of biochar, pyroligneous acids, and gas prepared from cotton stalk through a polygeneration process. Ind Crops Prod 170:113690. https://doi.org/10.1016/j.indcrop.2021.113690 Condeço JAD, Hariharakrishnan S, Ofili OM, et al (2021) Energetic valorisation of agricultural residues by solvent-based liquefaction. Biomass and Bioenergy 147. https://doi.org/10.1016/j.biombioe.2021.106003 da Silva CMS, da Boit MK, Lütke SF et al (2022) Pyrolysis of grape bagasse to produce char for Cu(II) adsorption: a circular economy perspective. Biomass Convers Biorefinery. https://doi.org/10.1007/s13399-022-02792-8 Dal Pozzo A, Armutlulu A, Rekhtina M et al (2019) CO2 Uptake and Cyclic Stability of MgO-Based CO2 Sorbents Promoted with Alkali Metal Nitrates and Their Eutectic Mixtures. ACS Appl Energy Mater 2:1295–1307. https://doi.org/10.1021/acsaem.8b01852 Demiral I, Ayan EA (2011) Pyrolysis of grape bagasse: Effect of pyrolysis conditions on the product yields and characterization of the liquid product. Bioresour Technol 102:3946–3951. https://doi.org/10.1016/j.biortech.2010.11.077 Diel JC, Franco DSP, Igansi AV, et al (2021a) Green synthesis of carbon nanotubes impregnated with metallic nanoparticles: Characterization and application in glyphosate adsorption. Chemosphere 283. https://doi.org/10.1016/j.chemosphere.2021.131193 Diel JC, Franco DSP, Nunes IDS, et al (2021b) Carbon nanotubes impregnated with metallic nanoparticles and their application as an adsorbent for the glyphosate removal in an aqueous matrix. J Environ Chem Eng 9. https://doi.org/10.1016/j.jece.2021.105178 Döscher H, Schmaltz T, Neef C, et al (2021) Graphene Roadmap Briefs (No. 2): industrialization status and prospects 2020. 2D Mater 8. https://doi.org/10.1088/2053-1583/abddcd |
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Atribución 4.0 Internacional (CC BY 4.0)© 2023, The Author(s)https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/closedAccesshttp://purl.org/coar/access_right/c_14cbSebem da Silva, Caroline MariaOliveira, Marcosvirtual::991-1Manera, ChristianGodinho, MarceloPerondi, DanieleAhmad, NaushadNawaz, AsadDotto, Guilherme LuizSilva, Luisvirtual::992-12025-04-04T14:53:59Z2025-04-04T14:53:59Z2023-11da Silva, C.M.S., Oliveira, M.L.S., Manera, C. et al. From grape bagasse to graphene-like porous carbon nanosheets for CO2 capture. Environ Sci Pollut Res 30, 113481–113493 (2023). https://doi.org/10.1007/s11356-023-30427-60944-1344https://hdl.handle.net/11323/1407510.1007/s11356-023-30427-61614-7499Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/Graphene-based materials have increasingly attracted attention in recent years. It is a material is recognized worldwide due to its numerous applications in several sectors. However, graphene production involves several challenges: scalability, high costs, and high-quality production. This study synthesized graphene-like porous carbon nanosheets (GPCNs) through a thermochemical process under a nitrogen atmosphere using grape bagasse as a precursor. Three temperatures (700, 800, and 900 ºC) of the pyrolysis process were studied. Chemical graphitization and activation were used to form high-specific surface area materials: FeCl3.6H2O(aq) and ZnCl2(s) in a simultaneous activation-graphitization (SAG) method. The materials obtained (GPCN700, GPCN800, and GPCN900) were compared to previously produced chars (C700, C800, and C900). A high specific surface area and total pore volume were obtained for GPCN materials, and GPCN900 presented the highest values: 1062.7 m2g−1 and 0.635 cm3 g−1, respectively. The GPCN and char materials were classified as mesoporous and applied as adsorbents for CO2(g). The GPCN800 presented the best CO2(g) adsorbent, with a CO2(g) adsorption capacity of 168.71 mg g−1.13 páginasapplication/pdfengSpringer NatureGermanyhttps://link.springer.com/article/10.1007/s11356-023-30427-6From grape bagasse to graphene-like porous carbon nanosheets for CO2 captureArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/version/c_970fb48d4fbd8a85Environmental Science and Pollution ResearchAcevedo S, Giraldo L, Moreno-Piraján JC (2020) Adsorption of CO2 on Activated Carbons Prepared by Chemical Activation with Cupric Nitrate. ACS Omega 5:10423–10432. https://doi.org/10.1021/acsomega.0c00342Aïssa B, Memon NK, Ali A, Khraisheh MK (2015) Recent progress in the growth and applications of graphene as a smart material: A review. Front Mater 2:1–19. https://doi.org/10.3389/fmats.2015.00058Faruque MA Al, Syduzzaman M, Sarkar J, et al (2021) A review on the production methods and applications of graphene-based materials. Nanomaterials 11. https://doi.org/10.3390/nano11092414Alcaraz L, López Fernández A, García-Díaz I, López FA (2018) Preparation and characterization of activated carbons from winemaking wastes and their adsorption of methylene blue. Adsorpt Sci Technol 36:1331–1351. https://doi.org/10.1177/0263617418770295Anderson TR, Hawkins E, Jones PD (2016) CO2, the greenhouse effect and global warming: from the pioneering work of Arrhenius and Callendar to today’s Earth System Models. Endeavour 40:178–187. https://doi.org/10.1016/j.endeavour.2016.07.002Ban CL, Xu Z, Wang D et al (2019) Porous Layered Carbon with Interconnected Pore Structure Derived from Reed Membranes for Supercapacitors. ACS Sustain Chem Eng 7:10742–10750. https://doi.org/10.1021/acssuschemeng.9b01429Benedetti V, Cordioli E, Patuzzi F, Baratieri M (2019) CO2 Adsorption study on pure and chemically activated chars derived from commercial biomass gasifiers. J CO2 Util 33:46–54. https://doi.org/10.1016/j.jcou.2019.05.008Benvenuti J, Fisch A, Dos Santos JHZ, Gutterres M (2019) Silica-based adsorbent material with grape bagasse encapsulated by the sol-gel method for the adsorption of Basic Blue 41 dye. J Environ Chem Eng 7:103342. https://doi.org/10.1016/j.jece.2019.103342Beres C, Costa GNS, Cabezudo I et al (2017) Towards integral utilization of grape pomace from winemaking process: A review. Waste Manag 68:581–594. https://doi.org/10.1016/j.wasman.2017.07.017Bhagiyalakshmi M, Lee JY, Jang HT (2010) Synthesis of mesoporous magnesium oxide: Its application to CO2 chemisorption. Int J Greenh Gas Control 4:51–56. https://doi.org/10.1016/j.ijggc.2009.08.001Boningari T, Inturi SNR, Manousiouthakis VI, Smirniotis PG (2018) Facile Synthesis of Flame Spray Pyrolysis-Derived Magnesium Oxide Nanoparticles for CO2 Sorption: Effect of Precursors, Morphology, and Structural Properties. Ind Eng Chem Res 57:9054–9061. https://doi.org/10.1021/acs.iecr.8b00188Brisebois PP, Siaj M (2020) Harvesting graphene oxide-years 1859 to 2019: A review of its structure, synthesis, properties and exfoliation. J Mater Chem C 8:1517–1547. https://doi.org/10.1039/c9tc03251gCandu N, Man I, Simion A et al (2019) Nitrogen-doped graphene as metal free basic catalyst for coupling reactions. J Catal 376:238–247. https://doi.org/10.1016/j.jcat.2019.07.011Chang B, Yin H, Zhang X et al (2017) Chemical blowing strategy synthesis of nitrogen-rich porous graphitized carbon nanosheets: Morphology, pore structure and supercapacitor application. Chem Eng J 312:191–203. https://doi.org/10.1016/j.cej.2016.11.129Cheng J, Hu SC, Sun GT et al (2021) The effect of pyrolysis temperature on the characteristics of biochar, pyroligneous acids, and gas prepared from cotton stalk through a polygeneration process. Ind Crops Prod 170:113690. https://doi.org/10.1016/j.indcrop.2021.113690Condeço JAD, Hariharakrishnan S, Ofili OM, et al (2021) Energetic valorisation of agricultural residues by solvent-based liquefaction. Biomass and Bioenergy 147. https://doi.org/10.1016/j.biombioe.2021.106003da Silva CMS, da Boit MK, Lütke SF et al (2022) Pyrolysis of grape bagasse to produce char for Cu(II) adsorption: a circular economy perspective. Biomass Convers Biorefinery. https://doi.org/10.1007/s13399-022-02792-8Dal Pozzo A, Armutlulu A, Rekhtina M et al (2019) CO2 Uptake and Cyclic Stability of MgO-Based CO2 Sorbents Promoted with Alkali Metal Nitrates and Their Eutectic Mixtures. ACS Appl Energy Mater 2:1295–1307. https://doi.org/10.1021/acsaem.8b01852Demiral I, Ayan EA (2011) Pyrolysis of grape bagasse: Effect of pyrolysis conditions on the product yields and characterization of the liquid product. Bioresour Technol 102:3946–3951. https://doi.org/10.1016/j.biortech.2010.11.077Diel JC, Franco DSP, Igansi AV, et al (2021a) Green synthesis of carbon nanotubes impregnated with metallic nanoparticles: Characterization and application in glyphosate adsorption. Chemosphere 283. https://doi.org/10.1016/j.chemosphere.2021.131193Diel JC, Franco DSP, Nunes IDS, et al (2021b) Carbon nanotubes impregnated with metallic nanoparticles and their application as an adsorbent for the glyphosate removal in an aqueous matrix. J Environ Chem Eng 9. https://doi.org/10.1016/j.jece.2021.105178Döscher H, Schmaltz T, Neef C, et al (2021) Graphene Roadmap Briefs (No. 2): industrialization status and prospects 2020. 2D Mater 8. https://doi.org/10.1088/2053-1583/abddcd11349311348130Carbon dioxideCharsGrape bagasseGraphene-like porous carbon nanosheetsPyrolysisPublication486b5991-6bbd-4f12-9907-dd19efe24611virtual::991-1f2872e80-7316-4a56-b020-995de6547b54virtual::992-1486b5991-6bbd-4f12-9907-dd19efe24611virtual::991-1f2872e80-7316-4a56-b020-995de6547b54virtual::992-10000-0002-7771-5085virtual::991-10000-0001-7678-9130virtual::992-1ORIGINALScopus - Print Document.pdfScopus - Print Document.pdfapplication/pdf226334https://repositorio.cuc.edu.co/bitstreams/acd83819-a865-4f5f-808f-36f755da4b7c/downloadb851524d77d5c95d1abb198e388f42caMD51LICENSElicense.txtlicense.txttext/plain; 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 públicamente en forma digital la Obra o cualquier Obra Derivada u Obra Colectiva, Usted debe mantener intacta toda la información de derecho de autor de la Obra y proporcionar, de forma razonable según el medio o manera que Usted esté utilizando: (i) el nombre del Autor Original si está provisto (o seudónimo, si fuere aplicable), y/o (ii) el nombre de la parte o las partes que el Autor Original y/o el Licenciante hubieren designado para la atribución (v.g., un instituto patrocinador, editorial, publicación) en la información de los derechos de autor del Licenciante, términos de servicios o de otras formas razonables; el título de la Obra si está provisto; en la medida de lo razonablemente factible y, si está provisto, el Identificador Uniforme de Recursos (Uniform Resource Identifier) que el Licenciante especifica para ser asociado con la Obra, salvo que tal URI no se refiera a la nota sobre los derechos de autor o a la información sobre el licenciamiento de la Obra; y en el caso de una Obra Derivada, atribuir el crédito identificando el uso de la Obra en la Obra Derivada (v.g., "Traducción Francesa de la Obra del Autor Original," o "Guión Cinematográfico basado en la Obra original del Autor Original"). Tal crédito puede ser implementado de cualquier forma razonable; en el caso, sin embargo, de Obras Derivadas u Obras Colectivas, tal crédito aparecerá, como mínimo, donde aparece el crédito de cualquier otro autor comparable y de una manera, al menos, tan destacada como el crédito de otro autor comparable.</li>
      <li>
        Para evitar toda confusión, el Licenciante aclara que, cuando la obra es una composición musical:
        <ol type="i">
          <li>Regalías por interpretación y ejecución bajo licencias generales. El Licenciante se reserva el derecho exclusivo de autorizar la ejecución pública o la ejecución pública digital de la obra y de recolectar, sea individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, SAYCO), las regalías por la ejecución pública o por la ejecución pública digital de la obra (por ejemplo Webcast) licenciada bajo licencias generales, si la interpretación o ejecución de la obra está primordialmente orientada por o dirigida a la obtención de una ventaja comercial o una compensación monetaria privada.</li>
          <li>Regalías por Fonogramas. El Licenciante se reserva el derecho exclusivo de recolectar, individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, los consagrados por la SAYCO), una agencia de derechos musicales o algún agente designado, las regalías por cualquier fonograma que Usted cree a partir de la obra (“versión cover”) y distribuya, en los términos del régimen de derechos de autor, si la creación o distribución de esa versión cover está primordialmente destinada o dirigida a obtener una ventaja comercial o una compensación monetaria privada.</li>
        </ol>
      </li>
      <li>Gestión de Derechos de Autor sobre Interpretaciones y Ejecuciones Digitales (WebCasting). Para evitar toda confusión, el Licenciante aclara que, cuando la obra sea un fonograma, el Licenciante se reserva el derecho exclusivo de autorizar la ejecución pública digital de la obra (por ejemplo, webcast) y de recolectar, individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, ACINPRO), las regalías por la ejecución pública digital de la obra (por ejemplo, webcast), sujeta a las disposiciones aplicables del régimen de Derecho de Autor, si esta ejecución pública digital está primordialmente dirigida a obtener una ventaja comercial o una compensación monetaria privada.</li>
    </ol>
  </li>
  <br/>
  <li>
    Representaciones, Garantías y Limitaciones de Responsabilidad.
    <p>A MENOS QUE LAS PARTES LO ACORDARAN DE OTRA FORMA POR ESCRITO, EL LICENCIANTE OFRECE LA OBRA (EN EL ESTADO EN EL QUE SE ENCUENTRA) “TAL CUAL”, SIN BRINDAR GARANTÍAS DE CLASE ALGUNA RESPECTO DE LA OBRA, YA SEA EXPRESA, IMPLÍCITA, LEGAL O CUALQUIERA OTRA, INCLUYENDO, SIN LIMITARSE A ELLAS, GARANTÍAS DE TITULARIDAD, COMERCIABILIDAD, ADAPTABILIDAD O ADECUACIÓN A PROPÓSITO DETERMINADO, AUSENCIA DE INFRACCIÓN, DE AUSENCIA DE DEFECTOS LATENTES O DE OTRO TIPO, O LA PRESENCIA O AUSENCIA DE ERRORES, SEAN O NO DESCUBRIBLES (PUEDAN O NO SER ESTOS DESCUBIERTOS). ALGUNAS JURISDICCIONES NO PERMITEN LA EXCLUSIÓN DE GARANTÍAS IMPLÍCITAS, EN CUYO CASO ESTA EXCLUSIÓN PUEDE NO APLICARSE A USTED.</p>
  </li>
  <br/>
  <li>
    Limitación de responsabilidad.
    <p>A MENOS QUE LO EXIJA EXPRESAMENTE LA LEY APLICABLE, EL LICENCIANTE NO SERÁ RESPONSABLE ANTE USTED POR DAÑO ALGUNO, SEA POR RESPONSABILIDAD EXTRACONTRACTUAL, PRECONTRACTUAL O CONTRACTUAL, OBJETIVA O SUBJETIVA, SE TRATE DE DAÑOS MORALES O PATRIMONIALES, DIRECTOS O INDIRECTOS, PREVISTOS O IMPREVISTOS PRODUCIDOS POR EL USO DE ESTA LICENCIA O DE LA OBRA, AUN CUANDO EL LICENCIANTE HAYA SIDO ADVERTIDO DE LA POSIBILIDAD DE DICHOS DAÑOS. ALGUNAS LEYES NO PERMITEN LA EXCLUSIÓN DE CIERTA RESPONSABILIDAD, EN CUYO CASO ESTA EXCLUSIÓN PUEDE NO APLICARSE A USTED.</p>
  </li>
  <br/>
  <li>
    Término.
    <ol type="a">
      <li>Esta Licencia y los derechos otorgados en virtud de ella terminarán automáticamente si Usted infringe alguna condición establecida en ella. Sin embargo, los individuos o entidades que han recibido Obras Derivadas o Colectivas de Usted de conformidad con esta Licencia, no verán terminadas sus licencias, siempre que estos individuos o entidades sigan cumpliendo íntegramente las condiciones de estas licencias. Las Secciones 1, 2, 5, 6, 7, y 8 subsistirán a cualquier terminación de esta Licencia.</li>
      <li>Sujeta a las condiciones y términos anteriores, la licencia otorgada aquí es perpetua (durante el período de vigencia de los derechos de autor de la obra). No obstante lo anterior, el Licenciante se reserva el derecho a publicar y/o estrenar la Obra bajo condiciones de licencia diferentes o a dejar de distribuirla en los términos de esta Licencia en cualquier momento; en el entendido, sin embargo, que esa elección no servirá para revocar esta licencia o que deba ser otorgada , bajo los términos de esta licencia), y esta licencia continuará en pleno vigor y efecto a menos que sea terminada como se expresa atrás. La Licencia revocada continuará siendo plenamente vigente y efectiva si no se le da término en las condiciones indicadas anteriormente.</li>
    </ol>
  </li>
  <br/>
  <li>
    Varios.
    <ol type="a">
      <li>Cada vez que Usted distribuya o ponga a disposición pública la Obra o una Obra Colectiva, el Licenciante ofrecerá al destinatario una licencia en los mismos términos y condiciones que la licencia otorgada a Usted bajo esta Licencia.</li>
      <li>Si alguna disposición de esta Licencia resulta invalidada o no exigible, según la legislación vigente, esto no afectará ni la validez ni la aplicabilidad del resto de condiciones de esta Licencia y, sin acción adicional por parte de los sujetos de este acuerdo, aquélla se entenderá reformada lo mínimo necesario para hacer que dicha disposición sea válida y exigible.</li>
      <li>Ningún término o disposición de esta Licencia se estimará renunciada y ninguna violación de ella será consentida a menos que esa renuncia o consentimiento sea otorgado por escrito y firmado por la parte que renuncie o consienta.</li>
      <li>Esta Licencia refleja el acuerdo pleno entre las partes respecto a la Obra aquí licenciada. No hay arreglos, acuerdos o declaraciones respecto a la Obra que no estén especificados en este documento. El Licenciante no se verá limitado por ninguna disposición adicional que pueda surgir en alguna comunicación emanada de Usted. Esta Licencia no puede ser modificada sin el consentimiento mutuo por escrito del Licenciante y Usted.</li>
    </ol>
  </li>
  <br/>
</ol>
 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