Development of a new formalism for oxygen catalysts design

我们打算开发一种新的形式主义的设计的电催化的基础上的ORR的电催化性能和催化剂的表面性质之间的相关性，使用第一性原理和它们的表面化学组成。这种方法将表明，材料的表面性质而不是体积性质是更适合于设计用于ORR的活性和选择性新催化剂的关键参数。我们将量化材料的表面化学组成和性质对其在酸性介质中的ORR活性的影响。该项目的主要研究方向（将平行进行）如下：1）通过理论计算（从头算模拟）确定Pd合金和其他过渡金属合金及其氧化物、氮化物或碳化物（钴合金、锰、钽合金、铜合金等）的各种组合的表面上的氧吸附和解吸能。以及建立它们的ORR性能与它们的体积和表面物理化学性质（化学组成、键类型、表面能、活性位点密度、形态等）之间的相关性; 2)这些材料的详细说明和电化学表征; 3）这些能量、基本原理、表面化学组成和用这些材料获得的ORR性能之间的相关性; 4）基于它们的表面性质将这些合金的ORR性能与铂的ORR性能进行比较;6）确定体积和表面性质的贡献; 7）建立可以整合表面性质对ORR活性的影响的形式体系; 8）识别形成新思想流派的基础的实验相关元素并验证其一致性; 9）验证实验事实与形式体系之间的联系，并潜在地确定必要的纠正措施; 10）用铂合金检验形式。这种方法开辟了一条新的思路，这将对电化学材料的经典思想流派构成重大挑战，这些思想流派将这些材料的性质与它们的体积性质联系起来。

We intend to develop a new formalism for the design of electro-catalysis based on the correlations between the electro- catalytic properties of the ORR and the surface properties of the catalysts using first principles and their surface chemical composition. This approach will show that surface properties rather than volume properties of materials are the key parameters which are more appropriate to design active and selective new catalysts for the ORR. We will quantify how is the effect of the surface chemical compositions and properties of materials on their ORR activity in an acid medium. The principal research directions of the project (to be carried out in parallel) are as follows: 1)determine by theoretical calculations (with ab initio simulation) of the oxygen adsorption and de-sorption energies on the surface of the various combinations of Pd-alloys and other transition-metal-alloys, their oxides, nitrides or Carbides (cobalt alloys, manganese, tantalum alloys, cupper alloys etc.) and establishment of the correlations between their performances for the ORR and their volume and surface physical-chemical properties (chemical composition, bond types, surface energies, active site density, morphology, etc.); 2) elaboration and electrochemical characterization of these materials; 3) correlations between these energies, the basic principles, the surface chemical composition  and the ORR performances obtained with these materials;  4)comparison of the performances of these alloys with those of platinum for the ORR based on their surface properties;6) determine the contribution of the volume and surface properties; 7) establishment of the formalism which may integrate the surface properties effect on the ORR activity; 8)identify the experimental correlation elements forming the basis for the new school of thought and verify their coherence; 9) verify the links between the experimental facts and the formalism, and potentially determine the necessary corrective actions; 10) test the formalism with Pt-alloys. This approach opens up a new line of thinking which will pose a significant challenge to the classical schools of thought on electrochemical materials that have linked the properties of these materials to their volume properties.