Titanate 페로브스카이트 형상에 따른 산소발생반응 영향에 대한 연구
Effects of Morphology Differences of Titanate Perovskites on Oxygen-evolution Reactions
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페로브스카이트 산화물로부터의 금속 나노입자를 용리하여 금속-산화물 복합촉매를 형성하는 기술은 산화물 표면에 금속 나노 입자가 균일하게 분포된 전기화학적 촉매를 설계하는데 활용되어 왔다. 본 연구에서는 페로브스카이트 형상에 따른 Ni 나노입자의 용리 및 산소발생반응 촉매 활성에미치는 영향을 조사하기 위해 정육면체 및 구형 Ni-doped CaTiO3를 합성하였다. 이전 연구를 통해 용매열 합성법에 의해 합성된 Ni-doped CaTiO3는 A-site에 Ni 이온들이 위치하는 것으로 나타났으며, 형성된 A-site 빈자리에 의해 OH–이 직접 치환되어 수화됨을 확인하였다. Ni 나노입자가 용리된 구형 입자는 Ni 나노 입자가 무작위로 분포되어 있는 반면, 큐브형상 입자는 가장자리를 따라 Ni 나노 입자가 용리되는 차이를 보여주었다. 소량의 Ni 함량(~4 mol%)을 가지는 구형및 큐브형상 촉매의 전류 밀도는 각각 1.7 V에서 ~10 mA cm–2 및 ~7 mA cm–2로 확인되었다. Tafel slope로부터 CaTiO3지지체의 A-site 빈자리 및 산소 화학량론비가 산소발생반응 중 양성자전도 측면에서 탈양성자 단계에 영향을 미칠 수 있다고 사료된다.
Abstract
Metal exsolution from perovskite oxides has been used to produce well-designed electro-catalysts where metal nanoparticles are homogeneously distributed on the surface of perovskites. In this study, we prepare cuboidal and spherical Ni-doped CaTiO3 to investigate the effects of the different perovskite morphologies on Ni exsolution and catalytic activity for OER. Ni ions seem to be incorporated into the A-site of CaTiO3 with structural OH ions via solvothermal route, and the stoichiometry of spheres and cubes were confirmed as (Ca0.82Ni0.04)Ti1O2.63(OH)0.46 and (Ca0.90Ni0.04)Ti1O2.88(OH)0.12, respectively. The spheres show random distribution of Ni nanoparticles along grain boundaries, whereas Ni nanoparticles are exsolved along the edges in the cubes. With the small amount of Ni contents (~4 mol%), geometric current density of each sphere and cube exhibits comparable OER activities of ~10 mA cm–2 and ~7 mA cm–2 at 1.7 V to previously reported catalysts such as transition metals or perovskites. We suppose from Tafel slope that different A-site and oxygen stoichiometry of the CaTiO3 may affect deprotonation step during OER in terms of proton conduction.
참고문헌 (27)
- K. Zeng, "Recent progress in alkaline water electrolysis for hydrogen production and applications", Prog. Energy Combust. Sci, 36(3), pp.307~326 (2010)
- L. Xiao, "First implementation of alkaline polymer electrolyte water electrolysis working only with pure water", Energy Environ. Sci, 5, pp.7869~7871 (2012)
- A. Manabe, "Basic study of alkaline water electrolysis", Electrochim. Acta, 100, pp.249~256 (2013)
- C. Hu, "Recent progress made in the mechanism comprehension and design of electrocatalysts for alkaline water splitting", Energy Environ. Sci, 12, pp.2620~2645 (2019)
- S. Jung, "Benchmarking nanoparticulate metal oxide electrocatalysts for the alkaline water oxidation reaction", J. Mater. Chem. A, 4, pp.3068~3076 (2016)
- L. C. Seitz, "A highly active and stable IrOx", SrIrO3 catalyst for the oxygen evolution reaction, 2016, pp.353, 1011~1014
- M. V. Ramos-Garcés, "Transition metal-modified exfoliated zirconium phosphate as an electrocatalyst for the oxygen evolution reaction", ACS Appl. Energy Mater, 2, pp.3561~3567 (2019)
- A. Grimaud, "Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution", Nat. Commun, 4, pp.2439~ (2013)
- X. Li, "Nickel based electrocatalysts for oxygen evolution in high current density, alkaline water electrolysers", Phys. Chem. Chem. Phys, 13, pp.1162~1167 (2011)
- J. G. Lee, "A new family of perovskite catalysts for oxygen-evolution reaction in alkaline media: BaNiO3 and BaNi0.83O2.5", J. Am. Chem. Soc, 138, pp.3541~3547 (2016)
- T. Maiyalagan, "Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions", Nat. Commun, 5, pp.3949~ (2014)
- M. Gong, "An advanced Ni−Fe layered double hydroxide electrocatalyst for water oxidation", J. Am. Chem. Soc, 135(23), pp.8452~8455 (2013)
- J. Zhang, "A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions", Nature Nanotech, 10, pp.444~452 (2015)
- J. Suntivich, "A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles", Science, 334, pp.1383~1385 (2011)
- J. T. Mefford, "Water electrolysis on La1−xSrxCoO3−δ perovskite electrocatalysts", Nat. Commun, 7, pp.11053~ (2016)
- B. K. Park, "Synthesis and size control of monodisperse copper nanoparticles by polyol method", J. Colloid Interface Sci, 311(2), pp.417~424 (2007)
- J. Myung, "Switching on electrocatalytic activity in solid oxide cells", Nature, 537, pp.528~531 (2016)
- D. Neagu, "Nano-socketed nickel particles with enhanced coking resistance grown in situ by redox exsolution", Nat. Commun, 6, pp.8120~ (2015)
- D. Neagu, "In situ growth of nanoparticles through control of non-stoichiometry", Nature Chem, 5, pp.916~923 (2013)
- G. Tsekouras, "Step-change in high temperature steam electrolysis performance of perovskite oxide cathodes with exsolution of B-site dopants", Energy Environ. Sci, 6, pp.256~266 (2013)
- J. G. Lee, "Replacement of Ca by Ni in a perovskite titanate to yield a novel perovskite exsolution architecture for oxygen-evolution reactions", Adv. Energy Mater, 10(10), pp.1903693~ (2020)
- X. Yang, "Formation mechanism of CaTiO3 hollow crystals with different microstructures", J. Am. Chem. Soc, 132(40), pp.14279~14287 (2010)
- B. Koo, "Sr segregation in perovskite oxides: Why it happens and how it exists", Joule, 2(8), pp.1476~1499 (2018)
- D. J. D. Corcoran, "Investigations into Sr3CaZr0.5Ta1.5O8.75, a novel proton conducting perovskite oxide", Solid State Ionics, 145(1–4), pp.307~313 (2001)
- Y. Lee, "Synthesis and activities of rutile IrO2 and RuO2nanoparticles for oxygen evolution in acid and alkaline solutions", J. Phys. Chem. Lett, 3(3), pp.399~404 (2012)
- G. Chen, "Two orders of magnitude enhancement in oxygen evolution reactivity on amorphous Ba0. 5Sr0. 5Co0. 8Fe0. 2O3-δ nanofilms with tunable oxidation state", Sci. Adv, 3, pp.e1603206~ (2019)
- C. Yang, "Phosphate ion functionalization of perovskite surfaces for enhanced oxygen evolution reaction", J. Phys. Chem. Lett, 8(15), pp.3466~3472 (2017)