Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: an experimental and computational study
The production of adipic acid (AA) from the ring-opening hydrogenolysis (hydrodeoxygenation - HDO) of tetrahydrofuran 2,5-dicarboxylic acid (THFDCA) by metal-metal oxide catalysts (Pt-MOx/TiO2 and Pt/MOx) was evaluated. Correlations between AA yield, or products distribution, and the type of active...
- Autores:
-
Castilla-Acevedo, Samir F.
Szobody, Titus P.
Boydston, Cameron M.
John, Jacob St.
Amaya-Roncancio, Sebastian
Allgeier, Alan M.
- Tipo de recurso:
- Article of investigation
- Fecha de publicación:
- 2024
- Institución:
- Corporación Universidad de la Costa
- Repositorio:
- REDICUC - Repositorio CUC
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.cuc.edu.co:11323/13938
- Acceso en línea:
- https://hdl.handle.net/11323/13938
https://repositorio.cuc.edu.co/
- Palabra clave:
- Metal-metal oxide catalysts
Hydrodeoxygenation
Biomass valorization
Furanic compounds
Carboxylic acid reduction
- Rights
- openAccess
- License
- Atribución 4.0 Internacional (CC BY 4.0)
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| dc.title.eng.fl_str_mv |
Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: an experimental and computational study |
| title |
Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: an experimental and computational study |
| spellingShingle |
Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: an experimental and computational study Metal-metal oxide catalysts Hydrodeoxygenation Biomass valorization Furanic compounds Carboxylic acid reduction |
| title_short |
Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: an experimental and computational study |
| title_full |
Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: an experimental and computational study |
| title_fullStr |
Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: an experimental and computational study |
| title_full_unstemmed |
Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: an experimental and computational study |
| title_sort |
Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: an experimental and computational study |
| dc.creator.fl_str_mv |
Castilla-Acevedo, Samir F. Szobody, Titus P. Boydston, Cameron M. John, Jacob St. Amaya-Roncancio, Sebastian Allgeier, Alan M. |
| dc.contributor.author.none.fl_str_mv |
Castilla-Acevedo, Samir F. Szobody, Titus P. Boydston, Cameron M. John, Jacob St. Amaya-Roncancio, Sebastian Allgeier, Alan M. |
| dc.subject.proposal.eng.fl_str_mv |
Metal-metal oxide catalysts Hydrodeoxygenation Biomass valorization Furanic compounds Carboxylic acid reduction |
| topic |
Metal-metal oxide catalysts Hydrodeoxygenation Biomass valorization Furanic compounds Carboxylic acid reduction |
| description |
The production of adipic acid (AA) from the ring-opening hydrogenolysis (hydrodeoxygenation - HDO) of tetrahydrofuran 2,5-dicarboxylic acid (THFDCA) by metal-metal oxide catalysts (Pt-MOx/TiO2 and Pt/MOx) was evaluated. Correlations between AA yield, or products distribution, and the type of active centers in the catalyst surface were established by studying the type (MOx: WOx, MoOx, and ZrOx), the amount of metal oxide (MOx:Pt molar ratio), and the reaction temperature (180ºC, 220ºC, and 240ºC) in Pt-MOx/TiO2 and Pt/MOx. The activity results show that only the catalysts that contain both Pt and Mo produced AA at 220ºC, with yields of 24 % for Pt-MoOx/TiO2 (4 wt % Pt, 1:1 Mo:Pt molar ratio) and 34% for 4 wt % Pt/MoO3. At 180ºC, these catalysts exhibited high selectivity towards reducing the carboxyl group. Computational studies using DFT suggest that this behavior is due to the preferential interaction between the oxygen vacancy (O-VAC) in MoO3 and the Cdouble bondO bond in the carboxyl group in 2-hydroxyadipic acid (2-HAA), the first observed intermediate from the HDO of THFDCA. Coverage of this adsorption configuration decreases at temperatures above 200ºC, where the interaction between the alcohol group in the 2 C position in 2-HAA and the Brønsted acid site (BAS) on the surface of MoO3 is preferred. This latter interaction could promote the acid-catalyzed dehydration of the alcohol group to obtain AA. Increasing the amount of Mo to 5:1 Mo:Pt in Pt-MoOx/TiO2 and decreasing the Pt content to 0.1 wt % in Pt/MoO3 decreases the selectivity to alcohols, increasing the AA yield to 55 % at 220ºC and 65 % at 240ºC for both catalysts. This enhancement in performance is consistent with the findings from the DFT studies. To our knowledge, this is the highest yield reported for AA production from THFDCA or FDCA by metal-metal oxide catalysts. |
| publishDate |
2024 |
| dc.date.issued.none.fl_str_mv |
2024-06-15 |
| dc.date.accessioned.none.fl_str_mv |
2025-01-21T14:26:35Z |
| dc.date.available.none.fl_str_mv |
2025-01-21T14:26:35Z |
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Artículo de revista |
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http://purl.org/coar/resource_type/c_2df8fbb1 |
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Samir F. Castilla-Acevedo, Titus P. Szobody, Cameron M. Boydston, Jacob St. John, Sebastian Amaya-Roncancio, Alan M. Allgeier, Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: An experimental and computational study, Catalysis Today, Volume 436, 2024, 114722, ISSN 0920-5861, https://doi.org/10.1016/j.cattod.2024.114722. |
| dc.identifier.uri.none.fl_str_mv |
https://hdl.handle.net/11323/13938 |
| dc.identifier.doi.none.fl_str_mv |
10.1016/j.cattod.2024.114722 |
| dc.identifier.eissn.none.fl_str_mv |
0920-5861 |
| dc.identifier.instname.none.fl_str_mv |
Corporación Universidad de la Costa |
| dc.identifier.reponame.none.fl_str_mv |
REDICUC - Repositorio CUC |
| dc.identifier.repourl.none.fl_str_mv |
https://repositorio.cuc.edu.co/ |
| identifier_str_mv |
Samir F. Castilla-Acevedo, Titus P. Szobody, Cameron M. Boydston, Jacob St. John, Sebastian Amaya-Roncancio, Alan M. Allgeier, Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: An experimental and computational study, Catalysis Today, Volume 436, 2024, 114722, ISSN 0920-5861, https://doi.org/10.1016/j.cattod.2024.114722. 10.1016/j.cattod.2024.114722 0920-5861 Corporación Universidad de la Costa REDICUC - Repositorio CUC |
| url |
https://hdl.handle.net/11323/13938 https://repositorio.cuc.edu.co/ |
| dc.language.iso.none.fl_str_mv |
eng |
| language |
eng |
| dc.relation.ispartofjournal.none.fl_str_mv |
Catalysis Today |
| dc.relation.references.none.fl_str_mv |
X. Jin, M. Liu, G. Zhang, J. Wang, Q. Xia, Y. Sun, Z. Zhou, W. Zhang, S. Wang, C.H. Lam, J. Shen, C. Yang, R.V. Chaudhari Chemical synthesis of adipic acid from glucose and derivatives: challenges for nanocatalyst design ACS Sustain Chem. Eng., 8 (2020), pp. 18732-18754, 10.1021/acssuschemeng.0c04411 J.C.J. Bart, S. Cavallaro Transiting from adipic acid to bioadipic acid. 1, petroleum-based processes Lucía Fernández, Market volume of adipic acid worldwide in 2018 and 2023, Statista (2021). Accessed 10/10/2023. Avinash D., Adipic Acid Market to Reach US$ 9.43 Billion by 2028, says the brainy insights, the brainy insights (2022). Accessed 10/10/2023. M. Lang, H. Li Sustainable Routes for the synthesis of renewable adipic acid from biomass derivatives ChemSusChem, 15 (1) (2022), p. 26, 10.1002/cssc.202101531 W. Yan, G. Zhang, J. Wang, M. Liu, Y. Sun, Z. Zhou, W. Zhang, S. Zhang, X. Xu, J. Shen, X. Jin Recent progress in adipic acid synthesis over heterogeneous catalysts Front Chem., 8 (2020), pp. 1-12, 10.3389/fchem.2020.00185 L. Wei, J. Zhang, W. Deng, S. Xie, Q. Zhang, Y. Wang Catalytic transformation of 2,5-furandicarboxylic acid to adipic acid over niobic acid-supported Pt nanoparticles Chem. Commun., 55 (2019), pp. 8013-8016, 10.1039/c9cc02877c M.J. Gilkey, H.J. Cho, B.M. Murphy, J. Wu, D.G. Vlachos, B. Xu Catalytic adipic acid production on zeolites from biomass-derived tetrahydrofuran-2,5-dicarboxylic acid ACS Appl. Energy Mater., 3 (2020), pp. 99-105, 10.1021/acsaem.9b01954 M.J. Gilkey, A.V. Mironenko, D.G. Vlachos, B. Xu Adipic acid production via metal-free selective hydrogenolysis of biomass-derived tetrahydrofuran-2,5-dicarboxylic acid ACS Catal., 7 (2017), pp. 6619-6634, 10.1021/acscatal.7b01753 A. Vy Tran, S. Park, H. Jin Lee, T. Yong Kim, Y. Kim, Y. Suh, K. Lee, Y. Jin Kim, J. Baek Efficient production of adipic acid by a two-step catalytic reaction of biomass-derived 2,5-furandicarboxylic acid ChemSusChem, 15 (2022), pp. 1-11, 10.1002/cssc.202200375 J.G. de Vries Catalytic conversion of renewable resources into bulk and fine chemicals Chem. Rec., 16 (2016), pp. 2783-2796, 10.1002/tcr.201600102 J. Fu, S. Liu, W. Zheng, R. Huang, C. Wang, A. Lawal, K. Alexopoulos, S. Liu, Y. Wang, K. Yu, J.A. Boscoboinik, Y. Liu, X. Liu, A.I. Frenkel, O.A. Abdelrahman, R.J. Gorte, S. Caratzoulas, D.G. Vlachos Modulating the dynamics of Brønsted acid sites on PtWOx inverse catalyst Nat. Catal., 5 (2022), pp. 144-153, 10.1038/s41929-022-00745-y M.J. Gilkey, R. Balakumar, D.G. Vlachos, B. Xu Adipic acid production catalyzed by a combination of a solid acid and an iodide salt from biomass-derived tetrahydrofuran-2,5-dicarboxylic acid Catal. Sci. Technol., 8 (2018), pp. 2661-2671, 10.1039/c8cy00379c J. Luo, M. Monai, H. Yun, L. Arroyo-Ramírez, C. Wang, C.B. Murray, P. Fornasiero, R.J. Gorte The H2 pressure dependence of hydrodeoxygenation selectivities for furfural over Pt/C catalysts Catal. Lett., 146 (2016), pp. 711-717, 10.1007/s10562-016-1705-x I.H. Choi, J.S. Lee, C.U. Kim, T.W. Kim, K.Y. Lee, K.R. Hwang Production of bio-jet fuel range alkanes from catalytic deoxygenation of Jatropha fatty acids on a WOx/Pt/TiO2 catalyst Fuel, 215 (2018), pp. 675-685, 10.1016/j.fuel.2017.11.094 X. Liang, B.S. Haynes, A. Montoya Acid-catalyzed ring opening of furan in aqueous solution Energy Fuels, 32 (2018), pp. 4139-4148, 10.1021/acs.energyfuels.7b03239 J. Hidalgo-Carrillo, A. Marinas, F.J. Urbano Chemistry of furfural and furanic derivatives Sustainable chemistry series, Furfural, World scientific (2018), pp. 1-30 Y. Nakagawa, M. Yabushita, K. Tomishige Reductive conversion of biomass-derived furancarboxylic acids with retention of carboxylic acid moiety Trans. Tianjin Univ., 27 (2021), pp. 165-179, 10.1007/s12209-021-00284-w T.R. Boussie, Dias L. Eric, Z.M. Fresco, J. Shoemaker, R. Archer, J. Hong, Production of Adipic Acid and Derivatives from Carbohydrate-Containing Materials, US 2010/0317823 A1, 2010. Y. Zhang, X. Guo, P. Tang, J. Xu Solubility of 2,5-furandicarboxylic acid in eight pure solvents and two binary solvent systems at 313.15–363.15 K J. Chem. Eng. Data, 63 (2018), pp. 1316-1324, 10.1021/acs.jced.7b00927 X. Li, P. Rui, T. Ye, X. Yao, R. Zhou, D. Li, S. Wang, J.H. Carter, G.J. Hutchings Hydrogenolysis of 5-hydroxymethylfurfural by in situ produced hydrogen from water on an iron catalyst Catal. Sci. Technol. (2023), pp. 3366-3374, 10.1039/D3CY00027C J. He, S.P. Burt, M. Ball, D. Zhao, I. Hermans, J.A. Dumesic, G.W. Huber Synthesis of 1,6-hexanediol from cellulose derived tetrahydrofuran-dimethanol with Pt-WOx/TiO2 catalysts ACS Catal., 8 (2018), pp. 1427-1439, 10.1021/acscatal.7b03593 T. Asano, Y. Nakagawa, M. Tamura, K. Tomishige Hydrogenolysis of tetrahydrofuran-2-carboxylic acid over tungsten-modified rhodium catalyst Appl. Catal. A Gen., 602 (2020), pp. 1-13, 10.1016/j.apcata.2020.117723 K.J. Stephens, A.M. Allgeier, A.L. Bell, T.R. Carlson, Y. Cheng, J.T. Douglas, L.A. Howe, C.A. Menning, S.A. Neuenswander, S.K. Sengupta, P.S. Thapa, J.C. Ritter A mechanistic study of polyol hydrodeoxygenation over a bifunctional Pt-WOx/TiO2 catalyst ACS Catal., 10 (2020), pp. 12996-13007, 10.1021/acscatal.0c03475 S. Fan, M. Zhang, H. Li Zirconium-doped enhanced the biomass hydrodeoxygenation over extremely low-loaded Pd catalysts Fuel, 315 (2022), Article 123060, 10.1016/j.fuel.2021.123060 T.N. Phan, Y.K. Park, I.G. Lee, C.H. Ko Enhancement of C–O bond cleavage to afford aromatics in the hydrodeoxygenation of anisole over ruthenium-supporting mesoporous metal oxides Appl. Catal. A Gen., 544 (2017), pp. 84-93, 10.1016/j.apcata.2017.06.029 M. Chia, Y.J. Pagán-Torres, D. Hibbitts, Q. Tan, H.N. Pham, A.K. Datye, M. Neurock, R.J. Davis, J.A. Dumesic Selective hydrogenolysis of polyols and cyclic ethers over bifunctional surface sites on rhodium-rhenium catalysts J. Am. Chem. Soc., 133 (2011), pp. 12675-12689, 10.1021/ja2038358 T. Asano, M. Tamura, Y. Nakagawa, K. Tomishige Selective hydrodeoxygenation of 2-furancarboxylic acid to valeric acid over molybdenum-oxide-modified platinum catalyst ACS Sustain Chem. Eng., 4 (2016), pp. 6253-6257, 10.1021/acssuschemeng.6b01640 Y. Takeda, M. Tamura, Y. Nakagawa, K. Okumura, K. Tomishige Characterization of Re-Pd/SiO2 catalysts for hydrogenation of stearic acid ACS Catal., 5 (2015), pp. 7034-7047, 10.1021/acscatal.5b01054 Y. Wu, S. Sourav, A. Worrad, J. Zhou, S. Caratzoulas, G. Tsilomelekis, W. Zheng, D.G. Vlachos Dynamic formation of Brønsted acid sites over supported WOx/Pt on SiO2 inverse catalysts─spectroscopy, probe chemistry, and calculations ACS Catal., 13 (2023), pp. 7371-7382, 10.1021/acscatal.3c00279 L.A. Gomez, R. Bababrik, M.R. Komarneni, J. Marlowe, T. Salavati-Fard, A.D. D’Amico, B. Wang, P. Christopher, S.P. Crossley Selective reduction of carboxylic acids to aldehydes with promoted MoO3 catalysts ACS Catal., 12 (2022), pp. 6313-6324, 10.1021/acscatal.2c01350 S. Brunauer, P.H. Emmett, E. Teller Adsorption of Gases in Multimolecular Layers J. Am. Chem. Soc., 60 (2) (1938), pp. 309-319, 10.1021/ja01269a023 P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, G.L. Chiarotti, M. Cococcioni, I. Dabo, A. Dal Corso, S. De Gironcoli, S. Fabris, G. Fratesi, R. Gebauer, U. Gerstmann, C. Gougoussis, A. Kokalj, M. Lazzeri, L. Martin-Samos, N. Marzari, F. Mauri, R. Mazzarello, S. Paolini, A. Pasquarello, L. Paulatto, C. Sbraccia, S. Scandolo, G. Sclauzero, A.P. Seitsonen, A. Smogunov, P. Umari, R.M. Wentzcovitch QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials J. Phys. Condens. Matter, 21 (2009), Article 395502, 10.1088/0953-8984/21/39/395502 A. Dal Corso, 〈http://pseudopotentials.quantum-espresso.org/legacy_tables/ps-library/w〉, (n.d.). Accessed 10/10/2023. J.P. Perdew, K. Burke, M. Ernzerhof Generalized gradient approximation made simple Phys. Rev. Lett., 77 (1996), pp. 3865-3868, 10.1103/PhysRevLett.77.3865 S. Grimme, J. Antony, S. Ehrlich, H. Krieg A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J. Chem. Phys., 132 (2010), 10.1063/1.3382344 S. Amaya-Roncancio, D.H. Linares, K. Sapag, M.I. Rojas Influence of coadsorbed H in CO dissociation and CHn formation on Fe (100): A DFT study Appl. Surf. Sci., 346 (2015), 10.1016/j.apsusc.2015.03.215 S. Amaya-Roncancio, D.H. Linares, H.A. Duarte, K. Sapag DFT study of hydrogen-assisted dissociation of CO by HCO, COH, and HCOH formation on Fe (100) J. Phys. Chem. C, 120 (2016), 10.1021/acs.jpcc.5b12014 H. Prats, L. Álvarez, F. Illas, R. Sayós Kinetic Monte Carlo simulations of the water gas shift reaction on Cu (111) from density functional theory-based calculations J. Catal., 333 (2016), pp. 217-226, 10.1016/j.jcat.2015.10.029 L. Tian, C.F. Huo, D.B. Cao, Y. Yang, J. Xu, B.S. Wu, H.W. Xiang, Y.Y. Xu, Y.W. Li Effects of reaction conditions on iron-catalyzed fischer-tropsch synthesis: a kinetic monte carlo study J. Mol. Struct.: THEOCHEM, 941 (2010), pp. 30-35, 10.1016/j.theochem.2009.10.032 M. Andersen, C. Panosetti, K. Reuter A practical guide to surface kinetic Monte Carlo simulations Front Chem., 7 (2019), 10.3389/fchem.2019.00202 T. Schablitzki, J. Rogal, R. Drautz A kinetic Monte Carlo approach to diffusion-controlled thermal desorption spectroscopy Philos. Trans. R. Soc. A: Math. Phys. Eng. Sci., 375 (2017), 10.1098/rsta.2016.0404 S. Pisduangdaw, O. Mekasuwandumrong, H. Yoshida, S.I. Fujita, M. Arai, J. Panpranot Flame-made Pt/TiO2 catalysts for the liquid-phase selective hydrogenation of 3-nitrostyrene Appl. Catal. A Gen., 490 (2015), pp. 193-200, 10.1016/j.apcata.2014.10.002 T. Prasomsri, T. Nimmanwudipong, Y. Román-Leshkov Effective hydrodeoxygenation of biomass-derived oxygenates into unsaturated hydrocarbons by MoO3 using low H2 pressures Energy Environ. Sci., 6 (2013), pp. 1732-1738, 10.1039/c3ee24360e A.J. Kohler, C.H. Walter, B.H. Shanks Kinetic analysis of the hydrodeoxygenation of aliphatic volatilized lignin molecules on bulk MoO3: elucidating the formation of alkenes and alkanes ACS Catal. (2023), pp. 14813-14827, 10.1021/acscatal.3c04444 L.O. Mark, A.H. Jenkins, H. Heinz, J.W. Medlin Furfuryl alcohol deoxygenation, decarbonylation, and ring-opening on Pt (111) Surf. Sci., 677 (2018), pp. 333-340, 10.1016/j.susc.2018.07.001 T. Toyao, S.M.A. Hakim Siddiki, K. Kon, K. ichi Shimizu The catalytic reduction of carboxylic acid derivatives and CO2 by metal nanoparticles on lewis-acidic supports Chem. Rec., 18 (2018), pp. 1374-1393, 10.1002/tcr.201800061 J.A. Lopez-Ruiz, R.J. Davis Decarbonylation of heptanoic acid over carbon-supported platinum nanoparticles Green. Chem., 16 (2014), pp. 683-694, 10.1039/c3gc41287c I. Song, H. Lee, S.W. Jeon, D.H. Kim Understanding the dynamic behavior of acid sites on TiO2-supported vanadia catalysts via operando DRIFTS under SCR-relevant conditions J. Catal., 382 (2020), pp. 269-279, 10.1016/j.jcat.2019.12.041 A. Mahdavi-Shakib, T.N. Whittaker, T.Y. Yun, K.B. Sravan Kumar, L.C. Rich, S. Wang, R.M. Rioux, L.C. Grabow, B.D. Chandler The role of surface hydroxyls in the entropy-driven adsorption and spillover of H2 on Au/TiO2 catalysts Nat. Catal. (2023), pp. 710-719, 10.1038/s41929-023-00996-3 S. Li, J.M. Hennigan, D.A. Dixon, K.A. Peterson Accurate thermochemistry for transition metal oxide clusters J. Phys. Chem. A, 113 (2009), pp. 7861-7877, 10.1021/jp810182a A. Ruiz Puigdollers, G. Pacchioni Reducibility of ZrO2/Pt3Zr and ZrO2/Pt 2D films compared to bulk zirconia: a DFT+U study of oxygen removal and H2 adsorption Nanoscale, 9 (2017), pp. 6866-6876, 10.1039/c7nr01904a D. Mei, A.M. Karim, Y. Wang Density functional theory study of acetaldehyde hydrodeoxygenation on MoO3 J. Phys. Chem. C, 115 (2011), pp. 8155-8164, 10.1021/jp200011j J. Zhou, A. Worrad, Y. Wang, K. Yu, S. Deshpande, J.A. Boscoboinik, S. Caratzoulas, W. Zheng, D.G. Vlachos The role of the metal core in the performance of WOx inverse catalysts Chem. Catal. (2023), Article 100756, 10.1016/j.checat.2023.100756 S. Najmi, M. Rasmussen, G. Innocenti, C. Chang, E. Stavitski, S.R. Bare, A.J. Medford, J.W. Medlin, C. Sievers Pretreatment effects on the surface chemistry of small oxygenates on molybdenum trioxide ACS Catal., 10 (2020), pp. 8187-8200, 10.1021/acscatal.0c01992 L. Karam, C.N. Neumann Heterogeneously catalyzed carboxylic acid hydrogenation to alcohols ChemCatChem, 14 (2022), pp. 1-18, 10.1002/cctc.202200953 A.R. Head, C. Gattinoni, L. Trotochaud, Y. Yu, O. Karslloǧlu, S. Pletincx, B. Eichhorn, H. Bluhm Water (Non-)Interaction with MoO3 J. Phys. Chem. C, 123 (2019), pp. 16836-16842, 10.1021/acs.jpcc.9b03822 D. Valencia, I. García-Cruz, L.F. Ramírez-Verduzco, J. Aburto Adsorption of biomass-derived products on MoO3: hydrogen bonding interactions under the spotlight ACS Omega, 3 (2018), pp. 14165-14172, 10.1021/acsomega.8b02497 T. Asano, Y. Nakagawa, M. Tamura, K. Tomishige Structure and mechanism of titania-supported platinum-molybdenum catalyst for hydrodeoxygenation of 2-furancarboxylic acid to valeric acid ACS Sustain Chem. Eng., 7 (2019), pp. 9601-9612, 10.1021/acssuschemeng.9b01104 |
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© 2024 The Authors. Published by Elsevier B.V. |
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Atribución 4.0 Internacional (CC BY 4.0) |
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Atribución 4.0 Internacional (CC BY 4.0)© 2024 The Authors. Published by Elsevier B.V.https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Castilla-Acevedo, Samir F.Szobody, Titus P.Boydston, Cameron M.John, Jacob St.Amaya-Roncancio, SebastianAllgeier, Alan M.2025-01-21T14:26:35Z2025-01-21T14:26:35Z2024-06-15Samir F. Castilla-Acevedo, Titus P. Szobody, Cameron M. Boydston, Jacob St. John, Sebastian Amaya-Roncancio, Alan M. Allgeier, Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: An experimental and computational study, Catalysis Today, Volume 436, 2024, 114722, ISSN 0920-5861, https://doi.org/10.1016/j.cattod.2024.114722.https://hdl.handle.net/11323/1393810.1016/j.cattod.2024.1147220920-5861Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/The production of adipic acid (AA) from the ring-opening hydrogenolysis (hydrodeoxygenation - HDO) of tetrahydrofuran 2,5-dicarboxylic acid (THFDCA) by metal-metal oxide catalysts (Pt-MOx/TiO2 and Pt/MOx) was evaluated. Correlations between AA yield, or products distribution, and the type of active centers in the catalyst surface were established by studying the type (MOx: WOx, MoOx, and ZrOx), the amount of metal oxide (MOx:Pt molar ratio), and the reaction temperature (180ºC, 220ºC, and 240ºC) in Pt-MOx/TiO2 and Pt/MOx. The activity results show that only the catalysts that contain both Pt and Mo produced AA at 220ºC, with yields of 24 % for Pt-MoOx/TiO2 (4 wt % Pt, 1:1 Mo:Pt molar ratio) and 34% for 4 wt % Pt/MoO3. At 180ºC, these catalysts exhibited high selectivity towards reducing the carboxyl group. Computational studies using DFT suggest that this behavior is due to the preferential interaction between the oxygen vacancy (O-VAC) in MoO3 and the Cdouble bondO bond in the carboxyl group in 2-hydroxyadipic acid (2-HAA), the first observed intermediate from the HDO of THFDCA. Coverage of this adsorption configuration decreases at temperatures above 200ºC, where the interaction between the alcohol group in the 2 C position in 2-HAA and the Brønsted acid site (BAS) on the surface of MoO3 is preferred. This latter interaction could promote the acid-catalyzed dehydration of the alcohol group to obtain AA. Increasing the amount of Mo to 5:1 Mo:Pt in Pt-MoOx/TiO2 and decreasing the Pt content to 0.1 wt % in Pt/MoO3 decreases the selectivity to alcohols, increasing the AA yield to 55 % at 220ºC and 65 % at 240ºC for both catalysts. This enhancement in performance is consistent with the findings from the DFT studies. To our knowledge, this is the highest yield reported for AA production from THFDCA or FDCA by metal-metal oxide catalysts.12 páginasapplication/pdfengElsevier B.V.Netherlandshttps://www.sciencedirect.com/science/article/pii/S0920586124002165Efficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts: an experimental and computational studyArtículo 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_970fb48d4fbd8a85Catalysis TodayX. Jin, M. Liu, G. Zhang, J. Wang, Q. Xia, Y. Sun, Z. Zhou, W. Zhang, S. Wang, C.H. Lam, J. Shen, C. Yang, R.V. Chaudhari Chemical synthesis of adipic acid from glucose and derivatives: challenges for nanocatalyst design ACS Sustain Chem. Eng., 8 (2020), pp. 18732-18754, 10.1021/acssuschemeng.0c04411J.C.J. Bart, S. Cavallaro Transiting from adipic acid to bioadipic acid. 1, petroleum-based processesLucía Fernández, Market volume of adipic acid worldwide in 2018 and 2023, Statista (2021). Accessed 10/10/2023.Avinash D., Adipic Acid Market to Reach US$ 9.43 Billion by 2028, says the brainy insights, the brainy insights (2022). Accessed 10/10/2023.M. Lang, H. Li Sustainable Routes for the synthesis of renewable adipic acid from biomass derivatives ChemSusChem, 15 (1) (2022), p. 26, 10.1002/cssc.202101531W. Yan, G. Zhang, J. Wang, M. Liu, Y. Sun, Z. Zhou, W. Zhang, S. Zhang, X. Xu, J. Shen, X. Jin Recent progress in adipic acid synthesis over heterogeneous catalysts Front Chem., 8 (2020), pp. 1-12, 10.3389/fchem.2020.00185L. Wei, J. Zhang, W. Deng, S. Xie, Q. Zhang, Y. Wang Catalytic transformation of 2,5-furandicarboxylic acid to adipic acid over niobic acid-supported Pt nanoparticles Chem. Commun., 55 (2019), pp. 8013-8016, 10.1039/c9cc02877cM.J. Gilkey, H.J. Cho, B.M. Murphy, J. Wu, D.G. Vlachos, B. Xu Catalytic adipic acid production on zeolites from biomass-derived tetrahydrofuran-2,5-dicarboxylic acid ACS Appl. Energy Mater., 3 (2020), pp. 99-105, 10.1021/acsaem.9b01954M.J. Gilkey, A.V. Mironenko, D.G. Vlachos, B. Xu Adipic acid production via metal-free selective hydrogenolysis of biomass-derived tetrahydrofuran-2,5-dicarboxylic acid ACS Catal., 7 (2017), pp. 6619-6634, 10.1021/acscatal.7b01753A. Vy Tran, S. Park, H. Jin Lee, T. Yong Kim, Y. Kim, Y. Suh, K. Lee, Y. Jin Kim, J. Baek Efficient production of adipic acid by a two-step catalytic reaction of biomass-derived 2,5-furandicarboxylic acid ChemSusChem, 15 (2022), pp. 1-11, 10.1002/cssc.202200375J.G. de Vries Catalytic conversion of renewable resources into bulk and fine chemicals Chem. Rec., 16 (2016), pp. 2783-2796, 10.1002/tcr.201600102J. Fu, S. Liu, W. Zheng, R. Huang, C. Wang, A. Lawal, K. Alexopoulos, S. Liu, Y. Wang, K. Yu, J.A. Boscoboinik, Y. Liu, X. Liu, A.I. Frenkel, O.A. Abdelrahman, R.J. Gorte, S. Caratzoulas, D.G. Vlachos Modulating the dynamics of Brønsted acid sites on PtWOx inverse catalyst Nat. Catal., 5 (2022), pp. 144-153, 10.1038/s41929-022-00745-yM.J. Gilkey, R. Balakumar, D.G. Vlachos, B. Xu Adipic acid production catalyzed by a combination of a solid acid and an iodide salt from biomass-derived tetrahydrofuran-2,5-dicarboxylic acid Catal. Sci. Technol., 8 (2018), pp. 2661-2671, 10.1039/c8cy00379cJ. Luo, M. Monai, H. Yun, L. Arroyo-Ramírez, C. Wang, C.B. Murray, P. Fornasiero, R.J. Gorte The H2 pressure dependence of hydrodeoxygenation selectivities for furfural over Pt/C catalysts Catal. Lett., 146 (2016), pp. 711-717, 10.1007/s10562-016-1705-xI.H. Choi, J.S. Lee, C.U. Kim, T.W. Kim, K.Y. Lee, K.R. Hwang Production of bio-jet fuel range alkanes from catalytic deoxygenation of Jatropha fatty acids on a WOx/Pt/TiO2 catalyst Fuel, 215 (2018), pp. 675-685, 10.1016/j.fuel.2017.11.094X. Liang, B.S. Haynes, A. Montoya Acid-catalyzed ring opening of furan in aqueous solution Energy Fuels, 32 (2018), pp. 4139-4148, 10.1021/acs.energyfuels.7b03239J. Hidalgo-Carrillo, A. Marinas, F.J. Urbano Chemistry of furfural and furanic derivatives Sustainable chemistry series, Furfural, World scientific (2018), pp. 1-30Y. Nakagawa, M. Yabushita, K. Tomishige Reductive conversion of biomass-derived furancarboxylic acids with retention of carboxylic acid moiety Trans. Tianjin Univ., 27 (2021), pp. 165-179, 10.1007/s12209-021-00284-wT.R. Boussie, Dias L. Eric, Z.M. Fresco, J. Shoemaker, R. Archer, J. Hong, Production of Adipic Acid and Derivatives from Carbohydrate-Containing Materials, US 2010/0317823 A1, 2010.Y. Zhang, X. Guo, P. Tang, J. Xu Solubility of 2,5-furandicarboxylic acid in eight pure solvents and two binary solvent systems at 313.15–363.15 K J. Chem. Eng. Data, 63 (2018), pp. 1316-1324, 10.1021/acs.jced.7b00927X. Li, P. Rui, T. Ye, X. Yao, R. Zhou, D. Li, S. Wang, J.H. Carter, G.J. Hutchings Hydrogenolysis of 5-hydroxymethylfurfural by in situ produced hydrogen from water on an iron catalyst Catal. Sci. Technol. (2023), pp. 3366-3374, 10.1039/D3CY00027CJ. He, S.P. Burt, M. Ball, D. Zhao, I. Hermans, J.A. Dumesic, G.W. Huber Synthesis of 1,6-hexanediol from cellulose derived tetrahydrofuran-dimethanol with Pt-WOx/TiO2 catalysts ACS Catal., 8 (2018), pp. 1427-1439, 10.1021/acscatal.7b03593T. Asano, Y. Nakagawa, M. Tamura, K. Tomishige Hydrogenolysis of tetrahydrofuran-2-carboxylic acid over tungsten-modified rhodium catalyst Appl. Catal. A Gen., 602 (2020), pp. 1-13, 10.1016/j.apcata.2020.117723K.J. Stephens, A.M. Allgeier, A.L. Bell, T.R. Carlson, Y. Cheng, J.T. Douglas, L.A. Howe, C.A. Menning, S.A. Neuenswander, S.K. Sengupta, P.S. Thapa, J.C. Ritter A mechanistic study of polyol hydrodeoxygenation over a bifunctional Pt-WOx/TiO2 catalyst ACS Catal., 10 (2020), pp. 12996-13007, 10.1021/acscatal.0c03475S. Fan, M. Zhang, H. Li Zirconium-doped enhanced the biomass hydrodeoxygenation over extremely low-loaded Pd catalysts Fuel, 315 (2022), Article 123060, 10.1016/j.fuel.2021.123060T.N. Phan, Y.K. Park, I.G. Lee, C.H. Ko Enhancement of C–O bond cleavage to afford aromatics in the hydrodeoxygenation of anisole over ruthenium-supporting mesoporous metal oxides Appl. Catal. A Gen., 544 (2017), pp. 84-93, 10.1016/j.apcata.2017.06.029M. Chia, Y.J. Pagán-Torres, D. Hibbitts, Q. Tan, H.N. Pham, A.K. Datye, M. Neurock, R.J. Davis, J.A. Dumesic Selective hydrogenolysis of polyols and cyclic ethers over bifunctional surface sites on rhodium-rhenium catalysts J. Am. Chem. Soc., 133 (2011), pp. 12675-12689, 10.1021/ja2038358T. Asano, M. Tamura, Y. Nakagawa, K. Tomishige Selective hydrodeoxygenation of 2-furancarboxylic acid to valeric acid over molybdenum-oxide-modified platinum catalyst ACS Sustain Chem. Eng., 4 (2016), pp. 6253-6257, 10.1021/acssuschemeng.6b01640Y. Takeda, M. Tamura, Y. Nakagawa, K. Okumura, K. Tomishige Characterization of Re-Pd/SiO2 catalysts for hydrogenation of stearic acid ACS Catal., 5 (2015), pp. 7034-7047, 10.1021/acscatal.5b01054Y. Wu, S. Sourav, A. Worrad, J. Zhou, S. Caratzoulas, G. Tsilomelekis, W. Zheng, D.G. Vlachos Dynamic formation of Brønsted acid sites over supported WOx/Pt on SiO2 inverse catalysts─spectroscopy, probe chemistry, and calculations ACS Catal., 13 (2023), pp. 7371-7382, 10.1021/acscatal.3c00279L.A. Gomez, R. Bababrik, M.R. Komarneni, J. Marlowe, T. Salavati-Fard, A.D. D’Amico, B. Wang, P. Christopher, S.P. Crossley Selective reduction of carboxylic acids to aldehydes with promoted MoO3 catalysts ACS Catal., 12 (2022), pp. 6313-6324, 10.1021/acscatal.2c01350S. Brunauer, P.H. Emmett, E. Teller Adsorption of Gases in Multimolecular Layers J. Am. Chem. Soc., 60 (2) (1938), pp. 309-319, 10.1021/ja01269a023P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, G.L. Chiarotti, M. Cococcioni, I. Dabo, A. Dal Corso, S. De Gironcoli, S. Fabris, G. Fratesi, R. Gebauer, U. Gerstmann, C. Gougoussis, A. Kokalj, M. Lazzeri, L. Martin-Samos, N. Marzari, F. Mauri, R. Mazzarello, S. Paolini, A. Pasquarello, L. Paulatto, C. Sbraccia, S. Scandolo, G. Sclauzero, A.P. Seitsonen, A. Smogunov, P. Umari, R.M. Wentzcovitch QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials J. Phys. Condens. Matter, 21 (2009), Article 395502, 10.1088/0953-8984/21/39/395502A. Dal Corso, 〈http://pseudopotentials.quantum-espresso.org/legacy_tables/ps-library/w〉, (n.d.). Accessed 10/10/2023.J.P. Perdew, K. Burke, M. Ernzerhof Generalized gradient approximation made simple Phys. Rev. Lett., 77 (1996), pp. 3865-3868, 10.1103/PhysRevLett.77.3865S. Grimme, J. Antony, S. Ehrlich, H. Krieg A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu J. Chem. Phys., 132 (2010), 10.1063/1.3382344S. Amaya-Roncancio, D.H. Linares, K. Sapag, M.I. Rojas Influence of coadsorbed H in CO dissociation and CHn formation on Fe (100): A DFT study Appl. Surf. Sci., 346 (2015), 10.1016/j.apsusc.2015.03.215S. Amaya-Roncancio, D.H. Linares, H.A. Duarte, K. Sapag DFT study of hydrogen-assisted dissociation of CO by HCO, COH, and HCOH formation on Fe (100) J. Phys. Chem. C, 120 (2016), 10.1021/acs.jpcc.5b12014H. Prats, L. Álvarez, F. Illas, R. Sayós Kinetic Monte Carlo simulations of the water gas shift reaction on Cu (111) from density functional theory-based calculations J. Catal., 333 (2016), pp. 217-226, 10.1016/j.jcat.2015.10.029L. Tian, C.F. Huo, D.B. Cao, Y. Yang, J. Xu, B.S. Wu, H.W. Xiang, Y.Y. Xu, Y.W. Li Effects of reaction conditions on iron-catalyzed fischer-tropsch synthesis: a kinetic monte carlo study J. Mol. Struct.: THEOCHEM, 941 (2010), pp. 30-35, 10.1016/j.theochem.2009.10.032M. Andersen, C. Panosetti, K. Reuter A practical guide to surface kinetic Monte Carlo simulations Front Chem., 7 (2019), 10.3389/fchem.2019.00202T. Schablitzki, J. Rogal, R. Drautz A kinetic Monte Carlo approach to diffusion-controlled thermal desorption spectroscopy Philos. Trans. R. Soc. A: Math. Phys. Eng. Sci., 375 (2017), 10.1098/rsta.2016.0404S. Pisduangdaw, O. Mekasuwandumrong, H. Yoshida, S.I. Fujita, M. Arai, J. Panpranot Flame-made Pt/TiO2 catalysts for the liquid-phase selective hydrogenation of 3-nitrostyrene Appl. Catal. A Gen., 490 (2015), pp. 193-200, 10.1016/j.apcata.2014.10.002T. Prasomsri, T. Nimmanwudipong, Y. Román-Leshkov Effective hydrodeoxygenation of biomass-derived oxygenates into unsaturated hydrocarbons by MoO3 using low H2 pressures Energy Environ. Sci., 6 (2013), pp. 1732-1738, 10.1039/c3ee24360eA.J. Kohler, C.H. Walter, B.H. Shanks Kinetic analysis of the hydrodeoxygenation of aliphatic volatilized lignin molecules on bulk MoO3: elucidating the formation of alkenes and alkanes ACS Catal. (2023), pp. 14813-14827, 10.1021/acscatal.3c04444L.O. Mark, A.H. Jenkins, H. Heinz, J.W. Medlin Furfuryl alcohol deoxygenation, decarbonylation, and ring-opening on Pt (111) Surf. Sci., 677 (2018), pp. 333-340, 10.1016/j.susc.2018.07.001T. Toyao, S.M.A. Hakim Siddiki, K. Kon, K. ichi Shimizu The catalytic reduction of carboxylic acid derivatives and CO2 by metal nanoparticles on lewis-acidic supports Chem. Rec., 18 (2018), pp. 1374-1393, 10.1002/tcr.201800061J.A. Lopez-Ruiz, R.J. Davis Decarbonylation of heptanoic acid over carbon-supported platinum nanoparticles Green. Chem., 16 (2014), pp. 683-694, 10.1039/c3gc41287cI. Song, H. Lee, S.W. Jeon, D.H. Kim Understanding the dynamic behavior of acid sites on TiO2-supported vanadia catalysts via operando DRIFTS under SCR-relevant conditions J. Catal., 382 (2020), pp. 269-279, 10.1016/j.jcat.2019.12.041A. Mahdavi-Shakib, T.N. Whittaker, T.Y. Yun, K.B. Sravan Kumar, L.C. Rich, S. Wang, R.M. Rioux, L.C. Grabow, B.D. Chandler The role of surface hydroxyls in the entropy-driven adsorption and spillover of H2 on Au/TiO2 catalysts Nat. Catal. (2023), pp. 710-719, 10.1038/s41929-023-00996-3S. Li, J.M. Hennigan, D.A. Dixon, K.A. Peterson Accurate thermochemistry for transition metal oxide clusters J. Phys. Chem. A, 113 (2009), pp. 7861-7877, 10.1021/jp810182aA. Ruiz Puigdollers, G. Pacchioni Reducibility of ZrO2/Pt3Zr and ZrO2/Pt 2D films compared to bulk zirconia: a DFT+U study of oxygen removal and H2 adsorption Nanoscale, 9 (2017), pp. 6866-6876, 10.1039/c7nr01904aD. Mei, A.M. Karim, Y. Wang Density functional theory study of acetaldehyde hydrodeoxygenation on MoO3 J. Phys. Chem. C, 115 (2011), pp. 8155-8164, 10.1021/jp200011jJ. Zhou, A. Worrad, Y. Wang, K. Yu, S. Deshpande, J.A. Boscoboinik, S. Caratzoulas, W. Zheng, D.G. Vlachos The role of the metal core in the performance of WOx inverse catalysts Chem. Catal. (2023), Article 100756, 10.1016/j.checat.2023.100756S. Najmi, M. Rasmussen, G. Innocenti, C. Chang, E. Stavitski, S.R. Bare, A.J. Medford, J.W. Medlin, C. Sievers Pretreatment effects on the surface chemistry of small oxygenates on molybdenum trioxide ACS Catal., 10 (2020), pp. 8187-8200, 10.1021/acscatal.0c01992L. Karam, C.N. Neumann Heterogeneously catalyzed carboxylic acid hydrogenation to alcohols ChemCatChem, 14 (2022), pp. 1-18, 10.1002/cctc.202200953A.R. Head, C. Gattinoni, L. Trotochaud, Y. Yu, O. Karslloǧlu, S. Pletincx, B. Eichhorn, H. Bluhm Water (Non-)Interaction with MoO3 J. Phys. Chem. C, 123 (2019), pp. 16836-16842, 10.1021/acs.jpcc.9b03822D. Valencia, I. García-Cruz, L.F. Ramírez-Verduzco, J. Aburto Adsorption of biomass-derived products on MoO3: hydrogen bonding interactions under the spotlight ACS Omega, 3 (2018), pp. 14165-14172, 10.1021/acsomega.8b02497T. Asano, Y. Nakagawa, M. Tamura, K. Tomishige Structure and mechanism of titania-supported platinum-molybdenum catalyst for hydrodeoxygenation of 2-furancarboxylic acid to valeric acid ACS Sustain Chem. Eng., 7 (2019), pp. 9601-9612, 10.1021/acssuschemeng.9b011041211147221873-4308Metal-metal oxide catalystsHydrodeoxygenationBiomass valorizationFuranic compoundsCarboxylic acid reductionPublicationORIGINALEfficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts.pdfEfficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts.pdfapplication/pdf2821970https://repositorio.cuc.edu.co/bitstreams/34f23ec6-a101-4997-94a8-ef0643637abd/downloadb9f6d7655d6e2ac78f8ddd5f25d395f6MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-815543https://repositorio.cuc.edu.co/bitstreams/ae95835d-67cb-45b6-810d-16c186afa9e1/download73a5432e0b76442b22b026844140d683MD52TEXTEfficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts.pdf.txtEfficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts.pdf.txtExtracted texttext/plain76045https://repositorio.cuc.edu.co/bitstreams/c489b408-9d1c-427c-a4cc-407cca3a655a/download2c7969eb866e4c401e72dde8904b7c8dMD53THUMBNAILEfficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts.pdf.jpgEfficient hydrodeoxygenation of tetrahydrofuran 2,5-dicarboxylic acid to adipic acid over Pt-MOx catalysts.pdf.jpgGenerated Thumbnailimage/jpeg14068https://repositorio.cuc.edu.co/bitstreams/737de8da-08bb-437f-b081-abf478f5fd46/download2d970152ee5ce7e402c3faaf000f150bMD5411323/13938oai:repositorio.cuc.edu.co:11323/139382025-01-22 04:00:48.67https://creativecommons.org/licenses/by/4.0/© 2024 The Authors. 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ara ejercer estos derechos sobre la Obra tal y como se indica a continuación:</p>
    <ol type="a">
      <li>Reproducir la Obra, incorporar la Obra en una o más Obras Colectivas, y reproducir la Obra incorporada en las Obras Colectivas.</li>
      <li>Distribuir copias o fonogramas de las Obras, exhibirlas públicamente, ejecutarlas públicamente y/o ponerlas a disposición pública, incluyéndolas como incorporadas en Obras Colectivas, según corresponda.</li>
      <li>Distribuir copias de las Obras Derivadas que se generen, exhibirlas públicamente, ejecutarlas públicamente y/o ponerlas a disposición pública.</li>
    </ol>
    <p>Los derechos mencionados anteriormente pueden ser ejercidos en todos los medios y formatos, actualmente conocidos o que se inventen en el futuro. Los derechos antes mencionados incluyen el derecho a realizar dichas modificaciones en la medida que sean técnicamente necesarias para ejercer los derechos en otro medio o formatos, pero de otra manera usted no está autorizado para realizar obras derivadas. Todos los derechos no otorgados expresamente por el Licenciante quedan por este medio reservados, incluyendo pero sin limitarse a aquellos que se mencionan en las secciones 4(d) y 4(e).</p>
  </li>
  <br/>
  <li>
    Restricciones.
    <p>La licencia otorgada en la anterior Sección 3 está expresamente sujeta y limitada por las siguientes restricciones:</p>
    <ol type="a">
      <li>Usted puede distribuir, exhibir públicamente, ejecutar públicamente, o poner a disposición pública la Obra sólo bajo las condiciones de esta Licencia, y Usted debe incluir una copia de esta licencia o del Identificador Universal de Recursos de la misma con cada copia de la Obra que distribuya, exhiba públicamente, ejecute públicamente o ponga a disposición pública. No es posible ofrecer o imponer ninguna condición sobre la Obra que altere o limite las condiciones de esta Licencia o el ejercicio de los derechos de los destinatarios otorgados en este documento. No es posible sublicenciar la Obra. Usted debe mantener intactos todos los avisos que hagan referencia a esta Licencia y a la cláusula de limitación de garantías. Usted no puede distribuir, exhibir públicamente, ejecutar públicamente, o poner a disposición pública la Obra con alguna medida tecnológica que controle el acceso o la utilización de ella de una forma que sea inconsistente con las condiciones de esta Licencia. Lo anterior se aplica a la Obra incorporada a una Obra Colectiva, pero esto no exige que la Obra Colectiva aparte de la obra misma quede sujeta a las condiciones de esta Licencia. Si Usted crea una Obra Colectiva, previo aviso de cualquier Licenciante debe, en la medida de lo posible, eliminar de la Obra Colectiva cualquier referencia a dicho Licenciante o al Autor Original, según lo solicitado por el Licenciante y conforme lo exige la cláusula 4(c).</li>
      <li>Usted no puede ejercer ninguno de los derechos que le han sido otorgados en la Sección 3 precedente de modo que estén principalmente destinados o directamente dirigidos a conseguir un provecho comercial o una compensación monetaria privada. El intercambio de la Obra por otras obras protegidas por derechos de autor, ya sea a través de un sistema para compartir archivos digitales (digital file-sharing) o de cualquier otra manera no será considerado como estar destinado principalmente o dirigido directamente a conseguir un provecho comercial o una compensación monetaria privada, siempre que no se realice un pago mediante una compensación monetaria en relación con el intercambio de obras protegidas por el derecho de autor.</li>
      <li>Si usted distribuye, exhibe públicamente, ejecuta públicamente o ejecuta 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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