†State Key laboratory of Heavy Oil Processing and Department of Materials Science and Engineering, China University of Petroleum, Beijing 102249, China.
‡Center for Electrochemistry, Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States.
J Am Chem Soc. 2015 Jun 17;137(23):7397-403. doi: 10.1021/jacs.5b03034. Epub 2015 Jun 5.
Both the ligand effect and surface strain can affect the electrocatalytic reactivity. In that matter exists a need to be fundamentally understood; however, there is no effective strategy to isolate the strain effect in electrocatalytic systems. In this research we show how the elastic strain in a platinum nanofilm varies the catalytic activity for the oxygen reduction reaction, a key barrier to the wide applications of fuel cells. NiTi shape memory alloy was selected as the substrate to strain engineer the deposited Pt nanofilm in both compressively and tensilely strained states by taking advantage of the two-way shape memory effect for the first time. We demonstrate that compressive strain weakens the Pt surface adsorption and hence improves the ORR activity, which reflects in a 52% enhancement of the kinetic rate constant and a 27 mV positive shift of the half-wave potential for the compressively strained 5 nm Pt compared to the pristine Pt. Tensile strain has the opposite effect, which is in general agreement with the proposed d-band theory.
配体效应和表面应变都会影响电催化反应活性。在这方面,我们需要从根本上加以理解;然而,在电催化体系中,还没有有效的策略来隔离应变效应。在这项研究中,我们展示了弹性应变如何改变铂纳米薄膜对氧还原反应的催化活性,氧还原反应是燃料电池广泛应用的关键障碍。我们选择镍钛形状记忆合金作为基底,首次利用其双向形状记忆效应,在压缩和拉伸应变状态下对沉积的 Pt 纳米薄膜进行应变工程。我们证明了压缩应变削弱了 Pt 表面吸附,从而提高了 ORR 活性,与原始 Pt 相比,压缩应变 5nmPt 的动力学速率常数提高了 52%,半波电位正移了 27mV。拉伸应变则产生相反的效果,这与所提出的 d 带理论大体一致。