Intolerance of the Ruddlesden–Popper La2NiO4+δ structure to A-site cation deficiency
Autor(a) principal: | |
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Data de Publicação: | 2023 |
Outros Autores: | , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10773/39703 |
Resumo: | Tuning cation nonstoichiometry is an effective approach to modify stability and functional properties and to assist surface redox engineering of perovskite oxides. This work addresses the possibility of the introduction of cation vacancies into the Ln sublattice of perovskite-related Ruddlesden-Popper Ln2NiO4+δ nickelates. La2-xNiO4±δ (x = 0-0.10) and Nd1.95NiO4±δ were selected as model compositions. Ceramic materials were sintered in air at 1350-1450°C for 10-40 h and characterized by the combination of experimental (XRD, ND, SEM, EDS, TGA, measurements of electrical transport properties) and computational (static lattice and molecular dynamics simulations) methods. All nominally A-site deficient materials comprised nickel oxide as a secondary phase. The fraction of NiO impurity in the La2-xNiO4±δ series increased with x, while the parameters of the orthorhombic crystal lattice remained composition-independent. Refinement of neutron diffraction patterns of La2NiO4+δ and La1.95NiO4±δ yielded the cation ratio La:Ni = 2:1 in the Ruddlesden-Popper phase for both materials. The results indicate that the concentration of cation vacancies that can be tolerated in the A sublattice of Ruddlesden-Popper La2NiO4+δ structure is ≪1 at.%, if any. The experimental findings are supported by the computer simulations showing that the formation of lanthanum-deficient La1.95NiO4 is energetically less favorable compared to cation-stoichiometric La2NiO4+δ co-existing with NiO or La4Ni3O10 secondary phases, and that introduction of lanthanum vacancy results in enhanced diffusivity of A-site cations at elevated temperatures and destabilization of Ruddlesden-Popper structure. Within experimental error, nominal cation deficiency had no effect on the electrical conductivity and oxygen permeability of La2-xNiO4±δ ceramics. |
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Intolerance of the Ruddlesden–Popper La2NiO4+δ structure to A-site cation deficiencyCrystal structurePerovskiteNonstoichiometryNeutron diffractionRuddlesden-Popper phaseFuel cellTuning cation nonstoichiometry is an effective approach to modify stability and functional properties and to assist surface redox engineering of perovskite oxides. This work addresses the possibility of the introduction of cation vacancies into the Ln sublattice of perovskite-related Ruddlesden-Popper Ln2NiO4+δ nickelates. La2-xNiO4±δ (x = 0-0.10) and Nd1.95NiO4±δ were selected as model compositions. Ceramic materials were sintered in air at 1350-1450°C for 10-40 h and characterized by the combination of experimental (XRD, ND, SEM, EDS, TGA, measurements of electrical transport properties) and computational (static lattice and molecular dynamics simulations) methods. All nominally A-site deficient materials comprised nickel oxide as a secondary phase. The fraction of NiO impurity in the La2-xNiO4±δ series increased with x, while the parameters of the orthorhombic crystal lattice remained composition-independent. Refinement of neutron diffraction patterns of La2NiO4+δ and La1.95NiO4±δ yielded the cation ratio La:Ni = 2:1 in the Ruddlesden-Popper phase for both materials. The results indicate that the concentration of cation vacancies that can be tolerated in the A sublattice of Ruddlesden-Popper La2NiO4+δ structure is ≪1 at.%, if any. The experimental findings are supported by the computer simulations showing that the formation of lanthanum-deficient La1.95NiO4 is energetically less favorable compared to cation-stoichiometric La2NiO4+δ co-existing with NiO or La4Ni3O10 secondary phases, and that introduction of lanthanum vacancy results in enhanced diffusivity of A-site cations at elevated temperatures and destabilization of Ruddlesden-Popper structure. Within experimental error, nominal cation deficiency had no effect on the electrical conductivity and oxygen permeability of La2-xNiO4±δ ceramics.American Chemical Society2024-10-10T00:00:00Z2023-10-10T00:00:00Z2023-10-10info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10773/39703eng0897-475610.1021/acs.chemmater.3c01594Bamburov, AleksandrNaumovich, YevgeniyKhalyavin, Dmitry D.Yaremchenko, Aleksey A.info:eu-repo/semantics/embargoedAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2024-02-22T12:17:42Zoai:ria.ua.pt:10773/39703Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-20T03:09:52.296222Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Intolerance of the Ruddlesden–Popper La2NiO4+δ structure to A-site cation deficiency |
title |
Intolerance of the Ruddlesden–Popper La2NiO4+δ structure to A-site cation deficiency |
spellingShingle |
Intolerance of the Ruddlesden–Popper La2NiO4+δ structure to A-site cation deficiency Bamburov, Aleksandr Crystal structure Perovskite Nonstoichiometry Neutron diffraction Ruddlesden-Popper phase Fuel cell |
title_short |
Intolerance of the Ruddlesden–Popper La2NiO4+δ structure to A-site cation deficiency |
title_full |
Intolerance of the Ruddlesden–Popper La2NiO4+δ structure to A-site cation deficiency |
title_fullStr |
Intolerance of the Ruddlesden–Popper La2NiO4+δ structure to A-site cation deficiency |
title_full_unstemmed |
Intolerance of the Ruddlesden–Popper La2NiO4+δ structure to A-site cation deficiency |
title_sort |
Intolerance of the Ruddlesden–Popper La2NiO4+δ structure to A-site cation deficiency |
author |
Bamburov, Aleksandr |
author_facet |
Bamburov, Aleksandr Naumovich, Yevgeniy Khalyavin, Dmitry D. Yaremchenko, Aleksey A. |
author_role |
author |
author2 |
Naumovich, Yevgeniy Khalyavin, Dmitry D. Yaremchenko, Aleksey A. |
author2_role |
author author author |
dc.contributor.author.fl_str_mv |
Bamburov, Aleksandr Naumovich, Yevgeniy Khalyavin, Dmitry D. Yaremchenko, Aleksey A. |
dc.subject.por.fl_str_mv |
Crystal structure Perovskite Nonstoichiometry Neutron diffraction Ruddlesden-Popper phase Fuel cell |
topic |
Crystal structure Perovskite Nonstoichiometry Neutron diffraction Ruddlesden-Popper phase Fuel cell |
description |
Tuning cation nonstoichiometry is an effective approach to modify stability and functional properties and to assist surface redox engineering of perovskite oxides. This work addresses the possibility of the introduction of cation vacancies into the Ln sublattice of perovskite-related Ruddlesden-Popper Ln2NiO4+δ nickelates. La2-xNiO4±δ (x = 0-0.10) and Nd1.95NiO4±δ were selected as model compositions. Ceramic materials were sintered in air at 1350-1450°C for 10-40 h and characterized by the combination of experimental (XRD, ND, SEM, EDS, TGA, measurements of electrical transport properties) and computational (static lattice and molecular dynamics simulations) methods. All nominally A-site deficient materials comprised nickel oxide as a secondary phase. The fraction of NiO impurity in the La2-xNiO4±δ series increased with x, while the parameters of the orthorhombic crystal lattice remained composition-independent. Refinement of neutron diffraction patterns of La2NiO4+δ and La1.95NiO4±δ yielded the cation ratio La:Ni = 2:1 in the Ruddlesden-Popper phase for both materials. The results indicate that the concentration of cation vacancies that can be tolerated in the A sublattice of Ruddlesden-Popper La2NiO4+δ structure is ≪1 at.%, if any. The experimental findings are supported by the computer simulations showing that the formation of lanthanum-deficient La1.95NiO4 is energetically less favorable compared to cation-stoichiometric La2NiO4+δ co-existing with NiO or La4Ni3O10 secondary phases, and that introduction of lanthanum vacancy results in enhanced diffusivity of A-site cations at elevated temperatures and destabilization of Ruddlesden-Popper structure. Within experimental error, nominal cation deficiency had no effect on the electrical conductivity and oxygen permeability of La2-xNiO4±δ ceramics. |
publishDate |
2023 |
dc.date.none.fl_str_mv |
2023-10-10T00:00:00Z 2023-10-10 2024-10-10T00:00:00Z |
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://hdl.handle.net/10773/39703 |
url |
http://hdl.handle.net/10773/39703 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
0897-4756 10.1021/acs.chemmater.3c01594 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/embargoedAccess |
eu_rights_str_mv |
embargoedAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
American Chemical Society |
publisher.none.fl_str_mv |
American Chemical Society |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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