Platinum (Pt) nanoparticle catalysts remain the most popular cathode materials for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. Non-metallic alloying of Pt has become an emerging strategy to improve electrocatalytic performance, however, the electrocatalytic ORR mechanisms still need to be understood for further improvement toward practical application. Herein, a rapid microwave reduction method is employed for alloying phosphorous (P) into Pt to form a carbon supported phosphorus-alloyed Pt nanoparticle catalyst (P-Pt/C), which demonstrates the ability to replace commercial Pt/C. By a combination of density functional theory calculations and in-situ electrochemical Raman spectroscopy, the regulation role of P-alloying in the electrocatalytic mechanisms is revealed. It is found that the nearby Pt atoms can convert the ORR pathway from associative one to dissociative one, exhibiting a spontaneous dissociation of *OOH intermediate to *OH and *O species as well as a change of potential determining step to *O protonation. Furthermore, the strategy of large-scale economic synthesis of such alloying Pt-based catalyst is also established, demonstrated by a gram-level synthesis per batch. This study puts insight into the electrocatalytic ORR fundamentals of Pt-alloying with non-metals and provides a basis for the reasonable design and synthesis of efficient nonmetals-alloyed Pt catalysts.
| 科 Family | 属数 Number of genus | 种数 Number of species | 占总种数比例 Percentage of total species (%) | 属 Genus | 种数 Number of species | 占总种数比例 Percentage of total species (%) |
|---|---|---|---|---|---|---|
| 鹅膏菌科Amanitaceae | 2 | 11 | 5.26 | 鹅膏菌属 Amanita | 10 | 4.78 |
| 小菇科 Mycenaceae | 2 | 12 | 5.74 | 丝盖伞属 Inocybe | 5 | 2.39 |
| 多孔菌科 Polyporaceae | 8 | 14 | 6.70 | 蜡蘑属 Laccaria | 5 | 2.39 |
| 红菇科 Russulaceae | 3 | 23 | 11.00 | 小皮伞属 Marasmius | 6 | 2.87 |
| 小菇属 Mycena | 11 | 5.26 | ||||
| 光柄菇属 Pluteus | 5 | 2.39 | ||||
| 红菇属 Russula | 17 | 8.13 | ||||
| 栓菌属 Trametes | 5 | 2.39 |