School of Chemistry and Molecular Engineering, East China Normal University , Shanghai 200241, China.
ACS Appl Mater Interfaces. 2017 Sep 27;9(38):32840-32850. doi: 10.1021/acsami.7b11229. Epub 2017 Sep 13.
A new porous covalent porphyrin framework (CPF) filled with triphenylphosphine was designed and synthesized using the rigid tetrakis(p-bromophenyl)porphyrin (TBPP) and 1,3,5-benzenetriboronic acid trivalent alcohol ester as building blocks. The carbonization of this special CPF has afforded coupled FeP and FeN nanoparticles embedded in N-doped carbons (FeP/FeN@N-doped carbons). This CPF serves as an "all in one" precursor of Fe, N, P, and C. The porous property and solid skeleton of the CPF endow FeP/FeN@N-doped carbons with porous structure and a high degree of graphitization. As a result, FeP/FeN@N-doped carbons exhibited highly efficient multifunctional electrocatalytic performance for water splitting and oxygen electroreduction. Typically, FeP/FeN@C-800, obtained at a heat-treatment temperature of 800 °C, showed an ORR half-wave potential of 0.80 V in alkaline media and 0.68 V in acidic media, close to that of commercial Pt/C catalysts. FeP/FeN@C-800 also displayed efficient OER and HER activities, comparable to other phosphide and nitride electrocatalysts. The coupled FeN and FeP nanoparticles embedded in carbons exert unique catalytic efficiency for water splitting and fuel cells.
一种新型的多孔共价卟啉骨架（CPF），其中填充了三苯基膦，是使用刚性四（对溴苯基）卟啉（TBPP）和 1,3,5-苯三硼酸三价醇酯作为构建块设计和合成的。这种特殊 CPF 的碳化提供了嵌入在氮掺杂碳中的耦合的 FeP 和 FeN 纳米颗粒（FeP/FeN@N-掺杂碳）。这种 CPF 作为 Fe、N、P 和 C 的“一体化”前体。CPF 的多孔性质和固态骨架赋予 FeP/FeN@N-掺杂碳多孔结构和高度石墨化。结果，FeP/FeN@N-掺杂碳在水分解和氧气电还原方面表现出高效的多功能电催化性能。典型地，在 800°C 的热处理温度下获得的 FeP/FeN@C-800 在碱性介质中表现出 0.80 V 的 ORR 半波电位，在酸性介质中表现出 0.68 V 的 ORR 半波电位，接近商业 Pt/C 催化剂。FeP/FeN@C-800 还表现出高效的 OER 和 HER 活性，可与其他磷化物和氮化物电催化剂相媲美。嵌入碳中的耦合的 FeN 和 FeP 纳米颗粒对水分解和燃料电池表现出独特的催化效率。
