Chen Hui, Shi Lei, Liang Xiao, Wang Lina, Asefa Tewodros, Zou Xiaoxin
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, China.
Department of Chemistry and Chemical Biology & Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, Piscataway, NJ, 08854, USA.
Angew Chem Int Ed Engl. 2020 Oct 26;59(44):19654-19658. doi: 10.1002/anie.202006756. Epub 2020 Jun 29.
Reducing the amount of iridium in oxygen evolution electrocatalysts without compromising their catalytic performances is one of the major requirements in proton-exchange-membrane water electrolyzers. Herein, with the help of theoretical studies, we show that anatase-type TiO -IrO solid solutions possess more active iridium catalytic sites for the oxygen evolution reaction (OER) than IrO , the benchmark OER catalyst. Note that the same is not observed for their rutile-type counterparts. However, owing to their thermodynamic metastability, anatase-type TiO -IrO solid solutions are generally hard to synthesize. Our theoretical studies demonstrate that such catalytically active anatase-type solid-solution phases can be created in situ on the surfaces of readily available SrTiO -SrIrO solid solutions during electrocatalysis in acidic solution as the solution can etch away Sr atoms. We experimentally show this with porous SrTiO -SrIrO solid-solution nanotubes synthesized by a facile synthetic route that contain 56 % less iridium than IrO yet show an order of magnitude higher apparent catalytic activity for OER in acidic solution.
在不降低催化性能的前提下减少析氧电催化剂中的铱含量是质子交换膜水电解槽的主要要求之一。在此,借助理论研究,我们表明,锐钛矿型TiO -IrO固溶体比基准析氧反应(OER)催化剂IrO具有更多用于析氧反应的活性铱催化位点。需要注意的是,金红石型的对应物并未观察到同样的情况。然而,由于其热力学亚稳定性,锐钛矿型TiO -IrO固溶体通常难以合成。我们的理论研究表明,在酸性溶液中进行电催化时,这种具有催化活性的锐钛矿型固溶体相可以在易于获得的SrTiO -SrIrO固溶体表面原位生成,因为该溶液可以蚀刻掉Sr原子。我们通过一种简便的合成路线合成了多孔SrTiO -SrIrO固溶体纳米管,实验证明了这一点,该纳米管中的铱含量比IrO少56%,但在酸性溶液中对OER的表观催化活性却高一个数量级。