CNR-ICCOM and IPCF, Consiglio Nazionale delle Ricerche via Giuseppe Moruzzi 1, 56124 Pisa (Italy); Materials and Process Simulation Center, California Institute of Technology, MC 139-74, Pasadena, CA 91125 (USA).
Angew Chem Int Ed Engl. 2014 Jun 23;53(26):6669-72. doi: 10.1002/anie.201403264. Epub 2014 May 14.
Hydrogen fuel cells (FC) are considered essential for a sustainable economy based on carbon-free energy sources, but a major impediment are the costs. First-principles quantum mechanics (density functional theory including solvation) is used to predict how the energies and barriers for the mechanistic steps of the oxygen reduction reaction (ORR) over the fcc(111) platinum surface depend on the dielectric constant of the solvent. The ORR kinetics can be strongly accelerated by decreasing the effective medium polarizability from the high value it has in water. Possible ways to realize this experimentally are suggested. The calculated volcano structure for the dependence of rate on solvent polarization is considered to be general, and should be observed in other electrochemical systems.
氢燃料电池（FC）被认为是基于无碳能源的可持续经济的关键，但主要障碍是成本。第一性原理量子力学（密度泛函理论包括溶剂化）用于预测在 fcc（111）铂表面上氧还原反应（ORR）的机理步骤的能量和势垒如何取决于溶剂的介电常数。通过降低有效介质极化率，可以大大加快 ORR 动力学，使其从水中的高值降低。提出了可能的实验实现方法。考虑到对溶剂极化依赖性的速率火山结构是普遍的，应该在其他电化学系统中观察到。
