界面溶剂化预先组织了析氧反应的过渡态
近日，德国马克斯·普朗克学会弗里茨-哈伯研究所Oener, Sebastian Z.团队揭示了界面溶剂化预先组织了析氧反应的过渡态。2025年9月3日，《自然-化学》杂志发表了这一成果。
析氧反应的缓慢动力学是水电解绿色制氢的能量瓶颈。反应在表面上进行，该表面经历了（从热）相变，以适应与偏置相关的多余电荷。
研究组对常见催化剂进行了Arrhenithem分析，并通过原位X射线吸收光谱和高能x射线衍射将活化能和指前因子与氧化物的结构适应性联系起来。他们观察到动力学从一个可能由界面溶剂化主导的机制转变为一个表面能量取代的机制。这发生在Ni（氧）氢氧化物的α或β相到γ-晶体结构之间的过渡电位和关键中间体的光谱指纹出现时。重要的是，这种转向电位与负载或表面积无关，而与催化剂的内在活性有关。这些结果表明，催化剂活性与初始界面溶剂化（前）步骤有内在联系。
附：英文原文
Title: Interfacial solvation pre-organizes the transition state of the oxygen evolution reaction
Author: Martnez-Hincapi, Ricardo, Timoshenko, Janis, Wagner, Timon, Ortega, Eduardo, Druce, Jody, Monteiro, Mariana C. O., Rscher, Martina, Jang, Joonbaek, Alagz, Elif yk, Lasagna, Samuele, Jacobse, Leon, Bergmann, Arno, Cuenya, Beatriz Roldan, Oener, Sebastian Z.
Issue&Volume: 2025-09-03
Abstract: The sluggish kinetics of the oxygen evolution reaction are an energetic bottleneck for green hydrogen production via water electrolysis. The reaction proceeds over a surface that undergoes (frustrated) phase transitions to accommodate bias-dependent excess charge. Here we perform Arrhenius analysis of common catalysts and correlate the activation energy and pre-exponential factor with the oxide’s structural adaptation via operando X-ray absorption spectroscopy and high-energy X-ray diffraction. We observe that the kinetics switch from a regime that is probably dominated by interfacial solvation to one where the surface energetics take over. This happens right at a transition potential between the α or β phases into the γ-crystal structure of Ni (oxy)hydroxides and when spectroscopic fingerprints of key intermediates emerge. Importantly, this turning potential is independent of the loading or the surface area and informs on the intrinsic catalyst activity. These results suggest that the catalyst activity is intrinsically linked to the initial interfacial solvation (pre-)step.
DOI: 10.1038/s41557-025-01932-7