Mei Jun, He Tianwei, Bai Juan, Qi Dongchen, Du Aijun, Liao Ting, Ayoko Godwin A, Yamauchi Yusuke, Sun Litao, Sun Ziqi
Centre for Materials Science, Queensland University of Technology, 2 George Street, Brisbane, QLD, 4000, Australia.
School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, QLD, 4000, Australia.
Adv Mater. 2021 Dec;33(49):e2104638. doi: 10.1002/adma.202104638. Epub 2021 Oct 8.
2D black phosphorus (BP) is one promising electrocatalyst toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalysis. The too strong adsorption of oxygen intermediates during OER, while the too weak adsorption of hydrogen intermediate during HER, however, greatly compromise its practical water splitting applications with overpotentials as high as 450 mV for OER and 420 mV for HER to achieve 10 mA cm under alkaline conditions. Herein, by rationally introducing the nanosized iridium (Ir) modifier together with optimized exposing surface toward electrolytes, an efficient Ir-modified BP electrocatalyst with much favorable adsorption energies toward catalytic intermediates possesses an outstanding pH-universal water splitting performance, surpassing the nearly all reported BP-based catalysts and the commercial noble-metal catalysts. The Ir-modified BP catalyst with the optimized exposed surfaces only requires an overall cell voltage of 1.54 and 1.57 V to achieve 10 mA cm in acidic and alkaline electrolysers, respectively. This design uncovers the potential applications of 2D BP in practical electrocatalysis fields via decreasing reaction intermediate adsorption energy barriers and promoting the interfacial electron coupling for heterostructured catalysts, and offers new insights into the surface-dependent activity enhancement mechanism.
二维黑磷（BP）是一种很有前景的用于析氢反应（HER）和析氧反应（OER）催化的电催化剂。然而，在OER过程中氧中间体的吸附过强，而在HER过程中氢中间体的吸附过弱，这极大地限制了其在实际水分解应用中的性能，在碱性条件下实现10 mA cm的电流密度时，OER的过电位高达450 mV，HER的过电位高达420 mV。在此，通过合理引入纳米尺寸的铱（Ir）修饰剂并优化面向电解质的暴露表面，一种对催化中间体具有更有利吸附能的高效Ir修饰BP电催化剂具有出色的pH通用水分解性能，超过了几乎所有报道的基于BP的催化剂和商业贵金属催化剂。具有优化暴露表面的Ir修饰BP催化剂在酸性和碱性电解槽中分别仅需1.54 V和1.57 V的电池总电压即可实现10 mA cm的电流密度。这种设计通过降低反应中间体吸附能垒和促进异质结构催化剂的界面电子耦合，揭示了二维BP在实际电催化领域的潜在应用，并为表面依赖性活性增强机制提供了新的见解。
