Synthesis and characterization of chromium silicate catalyst and its application in the gas phase glycerol transformation into acetaldehyde
Autor(a) principal: | |
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Data de Publicação: | 2020 |
Outros Autores: | , , , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1016/j.inoche.2019.107710 http://hdl.handle.net/11449/199806 |
Resumo: | Chromium silicates with MFI topology were hydrothermally synthesized, characterized, and applied as heterogeneous catalysts on the one-step gas-phase glycerol conversion into acetaldehyde and acrolein. The catalysts were characterized by XRD, SEM, FT-IR, ICP-OES, XPS, pyridine adsorption, nitrogen adsorption/desorption, and TGA. The experimental results showed that the use of chromium led to a zeolite containing surface-active species and framework chromium atoms, which were identified by XPS analysis, and named as Cr(1), Cr(2) and Cr(3) species. The catalytic reactions with CrMFI-H exhibited high glycerol conversion (97%), and the main products were acetaldehyde (30%) and acrolein (10%). The high yield of acetaldehyde was due to oxidation reactions taking place in Cr(3) species. A reaction pathway for the formation of acetaldehyde was proposed, and the DFT calculations corroborated the proposed mechanism. In comparison with MFI-H catalysts, reactions with CrMFI-H led to the formation or deposition of a negligible amount of coke (less than 3 wt%) either under O2 or N2 atmosphere. This study highlights the advantage of combining acid and redox sites in a single catalyst because the redox sites not only assist the selective conversion of glycerol but also participate in the oxidation of monomeric coke species before they polymerize and block the pores of the catalysts. |
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Synthesis and characterization of chromium silicate catalyst and its application in the gas phase glycerol transformation into acetaldehydeChromium silicates with MFI topology were hydrothermally synthesized, characterized, and applied as heterogeneous catalysts on the one-step gas-phase glycerol conversion into acetaldehyde and acrolein. The catalysts were characterized by XRD, SEM, FT-IR, ICP-OES, XPS, pyridine adsorption, nitrogen adsorption/desorption, and TGA. The experimental results showed that the use of chromium led to a zeolite containing surface-active species and framework chromium atoms, which were identified by XPS analysis, and named as Cr(1), Cr(2) and Cr(3) species. The catalytic reactions with CrMFI-H exhibited high glycerol conversion (97%), and the main products were acetaldehyde (30%) and acrolein (10%). The high yield of acetaldehyde was due to oxidation reactions taking place in Cr(3) species. A reaction pathway for the formation of acetaldehyde was proposed, and the DFT calculations corroborated the proposed mechanism. In comparison with MFI-H catalysts, reactions with CrMFI-H led to the formation or deposition of a negligible amount of coke (less than 3 wt%) either under O2 or N2 atmosphere. This study highlights the advantage of combining acid and redox sites in a single catalyst because the redox sites not only assist the selective conversion of glycerol but also participate in the oxidation of monomeric coke species before they polymerize and block the pores of the catalysts.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)São Paulo State University – UNESP Physics Department, Campus-São José do Rio PretoSão Paulo State University – UNESP Institute of Chemistry Biochemistry and Technology Department, Campus-AraraquaraSão Paulo State University – UNESP Department of Chemistry and Environmental Sciences, Campus-São José do Rio PretoSão Paulo State University – UNESP Physics Department, Campus-São José do Rio PretoSão Paulo State University – UNESP Institute of Chemistry Biochemistry and Technology Department, Campus-AraraquaraSão Paulo State University – UNESP Department of Chemistry and Environmental Sciences, Campus-São José do Rio PretoCNPq: 401679/2013-6CNPq: 473346/2012-5Universidade Estadual Paulista (Unesp)Luizon Filho, Roberto A. [UNESP]Possato, Luiz G. [UNESP]Santisteban, Oscar A.N. [UNESP]de Vasconcellos, Adriano [UNESP]da Silva, Danilo A. [UNESP]Lima, Marcelo F. [UNESP]Martins, Leandro [UNESP]Nery, José G. [UNESP]2020-12-12T01:49:48Z2020-12-12T01:49:48Z2020-02-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://dx.doi.org/10.1016/j.inoche.2019.107710Inorganic Chemistry Communications, v. 112.1387-7003http://hdl.handle.net/11449/19980610.1016/j.inoche.2019.1077102-s2.0-85076456032Scopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengInorganic Chemistry Communicationsinfo:eu-repo/semantics/openAccess2021-10-23T09:55:30Zoai:repositorio.unesp.br:11449/199806Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462021-10-23T09:55:30Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Synthesis and characterization of chromium silicate catalyst and its application in the gas phase glycerol transformation into acetaldehyde |
title |
Synthesis and characterization of chromium silicate catalyst and its application in the gas phase glycerol transformation into acetaldehyde |
spellingShingle |
Synthesis and characterization of chromium silicate catalyst and its application in the gas phase glycerol transformation into acetaldehyde Luizon Filho, Roberto A. [UNESP] |
title_short |
Synthesis and characterization of chromium silicate catalyst and its application in the gas phase glycerol transformation into acetaldehyde |
title_full |
Synthesis and characterization of chromium silicate catalyst and its application in the gas phase glycerol transformation into acetaldehyde |
title_fullStr |
Synthesis and characterization of chromium silicate catalyst and its application in the gas phase glycerol transformation into acetaldehyde |
title_full_unstemmed |
Synthesis and characterization of chromium silicate catalyst and its application in the gas phase glycerol transformation into acetaldehyde |
title_sort |
Synthesis and characterization of chromium silicate catalyst and its application in the gas phase glycerol transformation into acetaldehyde |
author |
Luizon Filho, Roberto A. [UNESP] |
author_facet |
Luizon Filho, Roberto A. [UNESP] Possato, Luiz G. [UNESP] Santisteban, Oscar A.N. [UNESP] de Vasconcellos, Adriano [UNESP] da Silva, Danilo A. [UNESP] Lima, Marcelo F. [UNESP] Martins, Leandro [UNESP] Nery, José G. [UNESP] |
author_role |
author |
author2 |
Possato, Luiz G. [UNESP] Santisteban, Oscar A.N. [UNESP] de Vasconcellos, Adriano [UNESP] da Silva, Danilo A. [UNESP] Lima, Marcelo F. [UNESP] Martins, Leandro [UNESP] Nery, José G. [UNESP] |
author2_role |
author author author author author author author |
dc.contributor.none.fl_str_mv |
Universidade Estadual Paulista (Unesp) |
dc.contributor.author.fl_str_mv |
Luizon Filho, Roberto A. [UNESP] Possato, Luiz G. [UNESP] Santisteban, Oscar A.N. [UNESP] de Vasconcellos, Adriano [UNESP] da Silva, Danilo A. [UNESP] Lima, Marcelo F. [UNESP] Martins, Leandro [UNESP] Nery, José G. [UNESP] |
description |
Chromium silicates with MFI topology were hydrothermally synthesized, characterized, and applied as heterogeneous catalysts on the one-step gas-phase glycerol conversion into acetaldehyde and acrolein. The catalysts were characterized by XRD, SEM, FT-IR, ICP-OES, XPS, pyridine adsorption, nitrogen adsorption/desorption, and TGA. The experimental results showed that the use of chromium led to a zeolite containing surface-active species and framework chromium atoms, which were identified by XPS analysis, and named as Cr(1), Cr(2) and Cr(3) species. The catalytic reactions with CrMFI-H exhibited high glycerol conversion (97%), and the main products were acetaldehyde (30%) and acrolein (10%). The high yield of acetaldehyde was due to oxidation reactions taking place in Cr(3) species. A reaction pathway for the formation of acetaldehyde was proposed, and the DFT calculations corroborated the proposed mechanism. In comparison with MFI-H catalysts, reactions with CrMFI-H led to the formation or deposition of a negligible amount of coke (less than 3 wt%) either under O2 or N2 atmosphere. This study highlights the advantage of combining acid and redox sites in a single catalyst because the redox sites not only assist the selective conversion of glycerol but also participate in the oxidation of monomeric coke species before they polymerize and block the pores of the catalysts. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020-12-12T01:49:48Z 2020-12-12T01:49:48Z 2020-02-01 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://dx.doi.org/10.1016/j.inoche.2019.107710 Inorganic Chemistry Communications, v. 112. 1387-7003 http://hdl.handle.net/11449/199806 10.1016/j.inoche.2019.107710 2-s2.0-85076456032 |
url |
http://dx.doi.org/10.1016/j.inoche.2019.107710 http://hdl.handle.net/11449/199806 |
identifier_str_mv |
Inorganic Chemistry Communications, v. 112. 1387-7003 10.1016/j.inoche.2019.107710 2-s2.0-85076456032 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Inorganic Chemistry Communications |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.source.none.fl_str_mv |
Scopus reponame:Repositório Institucional da UNESP instname:Universidade Estadual Paulista (UNESP) instacron:UNESP |
instname_str |
Universidade Estadual Paulista (UNESP) |
instacron_str |
UNESP |
institution |
UNESP |
reponame_str |
Repositório Institucional da UNESP |
collection |
Repositório Institucional da UNESP |
repository.name.fl_str_mv |
Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP) |
repository.mail.fl_str_mv |
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1799964723573161984 |