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改善析氧反应:钛酸盐钙钛矿催化剂上的析出钴纳米颗粒

Improving the Oxygen Evolution Reaction: Exsolved Cobalt Nanoparticles on Titanate Perovskite Catalyst.

作者信息

Zuo Shangshang, Liao Yuan, Wang Chenchen, Naden Aaron B, Irvine John T S

机构信息

School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK.

出版信息

Small. 2024 Mar;20(11):e2308867. doi: 10.1002/smll.202308867. Epub 2023 Oct 29.

Abstract

Perovskites are an important class of oxygen evolution reaction (OER) catalysts due to highly tunable compositions and adaptable characteristics. However, perovskite-based catalysts can have limited atom utilization efficiency due to large particle size, resulting in low mass activity. Herein, Cobalt nanoparticles are exsolved from La Ca Ti Co O perovskite and applied in OER. Upon reduction in the 5% H /N atmosphere at 800 °C for 2 h, the Co exsolved perovskite catalyst (R-LCTCo0.11) exhibits optimal OER performance. The mass activity of R-LCTCo0.11 reaches ≈1700 mA mg at an overpotential of 450 mV, which is 17 times and 3 times higher than that of LCTCo0.11 (97 mA mg ) and R-Mix (560 mA mg ) catalysts respectively, surpassing the benchmark catalyst RuO (42.7 mA mg of oxide at η = 470 mV). Electrochemical impedance spectroscopy (EIS) data reveals that R-LCTCo0.11 has the lowest charge transfer resistance (R  = 58 Ω), demonstrating the highest catalytic and kinetic activity for OER. Furthermore, this catalyst shows high stability during an accelerated durability test of 10 h electrolysis and 1000 cycles cyclic voltammetry (CV). This work demonstrates that nanoparticle exsolution from a doped perovskite is an effective strategy for improving the atom utilization efficiency in OER.

摘要

钙钛矿由于其高度可调的组成和适应性强的特性,是一类重要的析氧反应(OER)催化剂。然而,由于粒径较大,钙钛矿基催化剂的原子利用效率可能有限,导致质量活性较低。在此,钴纳米颗粒从La Ca Ti Co O钙钛矿中析出并应用于OER。在800°C的5%H /N气氛中还原2小时后,析出钴的钙钛矿催化剂(R-LCTCo0.11)表现出最佳的OER性能。R-LCTCo0.11在450 mV过电位下的质量活性达到约1700 mA mg,分别比LCTCo0.11(97 mA mg )和R-Mix(560 mA mg )催化剂高17倍和3倍,超过了基准催化剂RuO(在η = 470 mV时为42.7 mA mg的氧化物)。电化学阻抗谱(EIS)数据表明,R-LCTCo0.11具有最低的电荷转移电阻(R = 58 Ω),证明其对OER具有最高的催化和动力学活性。此外,在10小时电解和1000次循环伏安法(CV)的加速耐久性测试中,该催化剂表现出高稳定性。这项工作表明,从掺杂钙钛矿中析出纳米颗粒是提高OER中原子利用效率的有效策略。

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