Defective Ru-doped α-MnO2 nanorods enabling efficient hydrazine oxidation for energy-saving hydrogen production via proton exchange membranes at near-neutral pH
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/10400.22/23529 |
Resumo: | Proton exchange membrane water electrolysis (PEMWE) showes substantial advantages over the conventional alkaline water electrolysis (AWE) for power-to-hydrogen (PtH) conversion, given the faster response and wider dynamic current range of the PEMWE technology. However, PEMWE is currently still expensive due partly to the high voltage needed to operate at high current densities and inevitable usage of precious iridium/rutheniumbased catalysts to expedite the slow kinetics of the oxygen evolution reaction (OER) and to ensure sufficient durability under strongly acidic conditions. Herein, we report that ruthenium doped α-manganese oxide (Ru/ α-MnO2) nanorods show outstanding electrocatalytic performance toward the hydrazine (N2H4) oxidation reaction (HzOR) in near-neutral media (weak alkaline and weak acid), which can be used to replace the energydemanding OER for PEMWE. The as-prepared Ru/α-MnO2 is found to comprise abundant defects. When used to catalyze HzOR in the acid-hydrazine electrolyte (0.05 M H2SO4 + 0.5 M N2H4), it can deliver an anodic current density of 10 mA cm 2 at a potential as low as 0.166 V vs. reversible hydrogen electrode (RHE). Moreover, Ru/ α-MnO2 exhibits remarkable corrosion/oxidation resistance and remains electrochemically stable during HzOR for at least 1000 h. Theoretical calculations and experimental studies prove that Ru doping elongates the Mn–O bond and produces abundant cationic defects, which induces charge delocalization and significantly lowers material’s electrical resistance and overpotential, resulting in excellent HzOR catalytic activity and stability. The introduction of N2H4 significantly reduces the energy demand for hydrogen production, so that PEMWE can be accomplished under remarkably low voltages of 0.254 V at 10 mA cm 2 and 0.935 V at 100 mA cm 2 for a long term without notable degradation. This work opens a new avenue toward energy-saving PEMWE with earthabundant OER catalysts. |
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Defective Ru-doped α-MnO2 nanorods enabling efficient hydrazine oxidation for energy-saving hydrogen production via proton exchange membranes at near-neutral pHCationic defectRu dopingPEM water electrolysisHydrazine oxidation reactionElectrocatalysisProton exchange membrane water electrolysis (PEMWE) showes substantial advantages over the conventional alkaline water electrolysis (AWE) for power-to-hydrogen (PtH) conversion, given the faster response and wider dynamic current range of the PEMWE technology. However, PEMWE is currently still expensive due partly to the high voltage needed to operate at high current densities and inevitable usage of precious iridium/rutheniumbased catalysts to expedite the slow kinetics of the oxygen evolution reaction (OER) and to ensure sufficient durability under strongly acidic conditions. Herein, we report that ruthenium doped α-manganese oxide (Ru/ α-MnO2) nanorods show outstanding electrocatalytic performance toward the hydrazine (N2H4) oxidation reaction (HzOR) in near-neutral media (weak alkaline and weak acid), which can be used to replace the energydemanding OER for PEMWE. The as-prepared Ru/α-MnO2 is found to comprise abundant defects. When used to catalyze HzOR in the acid-hydrazine electrolyte (0.05 M H2SO4 + 0.5 M N2H4), it can deliver an anodic current density of 10 mA cm 2 at a potential as low as 0.166 V vs. reversible hydrogen electrode (RHE). Moreover, Ru/ α-MnO2 exhibits remarkable corrosion/oxidation resistance and remains electrochemically stable during HzOR for at least 1000 h. Theoretical calculations and experimental studies prove that Ru doping elongates the Mn–O bond and produces abundant cationic defects, which induces charge delocalization and significantly lowers material’s electrical resistance and overpotential, resulting in excellent HzOR catalytic activity and stability. The introduction of N2H4 significantly reduces the energy demand for hydrogen production, so that PEMWE can be accomplished under remarkably low voltages of 0.254 V at 10 mA cm 2 and 0.935 V at 100 mA cm 2 for a long term without notable degradation. This work opens a new avenue toward energy-saving PEMWE with earthabundant OER catalysts.L. Liu acknowledges the start-up grant of the Songshan Lake Materials Laboratory (Grant No. Y2D1051Z311) and financial support from the Ministry of Science & Technology of China (Grant No. 22J4021Z311). B. Li is supported by Natural Science Foundation of Liao Ning Province (2021-MS-004) and ShenYang Normal University (BS202208). Z. P. Yu is financially supported by the China Scholarship Council (Grant No. 201806150015). Additionally, this work was also partially supported by the National Innovation Agency of Portugal through the Mobilizador project (Baterias 2030, Grant No. POCI-01-0247-FEDER-046109).ElsevierRepositório Científico do Instituto Politécnico do PortoYu, ZhipengSi, ChaoweiSabaté, FerranLaGrow, Alec P.Tai, ZhixinDiaconescu, Vlad MartinSimonelli, LauraMeng, LijianSabater, Maria J.Li, BoLiu, Lifeng2023-08-152031-01-01T00:00:00Z2023-08-15T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.22/23529eng10.1016/j.cej.2023.144050metadata only accessinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2023-09-20T01:46:03Zoai:recipp.ipp.pt:10400.22/23529Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:29:41.424190Repositório 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 |
Defective Ru-doped α-MnO2 nanorods enabling efficient hydrazine oxidation for energy-saving hydrogen production via proton exchange membranes at near-neutral pH |
title |
Defective Ru-doped α-MnO2 nanorods enabling efficient hydrazine oxidation for energy-saving hydrogen production via proton exchange membranes at near-neutral pH |
spellingShingle |
Defective Ru-doped α-MnO2 nanorods enabling efficient hydrazine oxidation for energy-saving hydrogen production via proton exchange membranes at near-neutral pH Yu, Zhipeng Cationic defect Ru doping PEM water electrolysis Hydrazine oxidation reaction Electrocatalysis |
title_short |
Defective Ru-doped α-MnO2 nanorods enabling efficient hydrazine oxidation for energy-saving hydrogen production via proton exchange membranes at near-neutral pH |
title_full |
Defective Ru-doped α-MnO2 nanorods enabling efficient hydrazine oxidation for energy-saving hydrogen production via proton exchange membranes at near-neutral pH |
title_fullStr |
Defective Ru-doped α-MnO2 nanorods enabling efficient hydrazine oxidation for energy-saving hydrogen production via proton exchange membranes at near-neutral pH |
title_full_unstemmed |
Defective Ru-doped α-MnO2 nanorods enabling efficient hydrazine oxidation for energy-saving hydrogen production via proton exchange membranes at near-neutral pH |
title_sort |
Defective Ru-doped α-MnO2 nanorods enabling efficient hydrazine oxidation for energy-saving hydrogen production via proton exchange membranes at near-neutral pH |
author |
Yu, Zhipeng |
author_facet |
Yu, Zhipeng Si, Chaowei Sabaté, Ferran LaGrow, Alec P. Tai, Zhixin Diaconescu, Vlad Martin Simonelli, Laura Meng, Lijian Sabater, Maria J. Li, Bo Liu, Lifeng |
author_role |
author |
author2 |
Si, Chaowei Sabaté, Ferran LaGrow, Alec P. Tai, Zhixin Diaconescu, Vlad Martin Simonelli, Laura Meng, Lijian Sabater, Maria J. Li, Bo Liu, Lifeng |
author2_role |
author author author author author author author author author author |
dc.contributor.none.fl_str_mv |
Repositório Científico do Instituto Politécnico do Porto |
dc.contributor.author.fl_str_mv |
Yu, Zhipeng Si, Chaowei Sabaté, Ferran LaGrow, Alec P. Tai, Zhixin Diaconescu, Vlad Martin Simonelli, Laura Meng, Lijian Sabater, Maria J. Li, Bo Liu, Lifeng |
dc.subject.por.fl_str_mv |
Cationic defect Ru doping PEM water electrolysis Hydrazine oxidation reaction Electrocatalysis |
topic |
Cationic defect Ru doping PEM water electrolysis Hydrazine oxidation reaction Electrocatalysis |
description |
Proton exchange membrane water electrolysis (PEMWE) showes substantial advantages over the conventional alkaline water electrolysis (AWE) for power-to-hydrogen (PtH) conversion, given the faster response and wider dynamic current range of the PEMWE technology. However, PEMWE is currently still expensive due partly to the high voltage needed to operate at high current densities and inevitable usage of precious iridium/rutheniumbased catalysts to expedite the slow kinetics of the oxygen evolution reaction (OER) and to ensure sufficient durability under strongly acidic conditions. Herein, we report that ruthenium doped α-manganese oxide (Ru/ α-MnO2) nanorods show outstanding electrocatalytic performance toward the hydrazine (N2H4) oxidation reaction (HzOR) in near-neutral media (weak alkaline and weak acid), which can be used to replace the energydemanding OER for PEMWE. The as-prepared Ru/α-MnO2 is found to comprise abundant defects. When used to catalyze HzOR in the acid-hydrazine electrolyte (0.05 M H2SO4 + 0.5 M N2H4), it can deliver an anodic current density of 10 mA cm 2 at a potential as low as 0.166 V vs. reversible hydrogen electrode (RHE). Moreover, Ru/ α-MnO2 exhibits remarkable corrosion/oxidation resistance and remains electrochemically stable during HzOR for at least 1000 h. Theoretical calculations and experimental studies prove that Ru doping elongates the Mn–O bond and produces abundant cationic defects, which induces charge delocalization and significantly lowers material’s electrical resistance and overpotential, resulting in excellent HzOR catalytic activity and stability. The introduction of N2H4 significantly reduces the energy demand for hydrogen production, so that PEMWE can be accomplished under remarkably low voltages of 0.254 V at 10 mA cm 2 and 0.935 V at 100 mA cm 2 for a long term without notable degradation. This work opens a new avenue toward energy-saving PEMWE with earthabundant OER catalysts. |
publishDate |
2023 |
dc.date.none.fl_str_mv |
2023-08-15 2023-08-15T00:00:00Z 2031-01-01T00:00:00Z |
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/10400.22/23529 |
url |
http://hdl.handle.net/10400.22/23529 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
10.1016/j.cej.2023.144050 |
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metadata only access info:eu-repo/semantics/openAccess |
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metadata only access |
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openAccess |
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application/pdf |
dc.publisher.none.fl_str_mv |
Elsevier |
publisher.none.fl_str_mv |
Elsevier |
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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) |
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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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