CAJ | 학술논문

目的：制备一种具有高稳定性和高催化活性的Pt/C@PANI“核/壳”结构催化剂。方法利用原位化学氧化聚合法制备聚苯胺修饰Pt/C@PANI“核/壳”结构催化剂,采用循环伏安加速寿命实验,结合电化学活性表面积、氧还原活性、X-射线光电子能谱和透射电镜,考察所制备催化剂的活性和稳定性,通过密度泛函理论探究PANI增强Pt/C催化剂活性和稳定性的量子化学本质原因。结果电化学测试表明,Pt/C@PANI催化剂的催化活性与聚苯胺包覆层含量和厚度密切相关,Pt/C@PANI(30%)催化剂具有最好的催化活性,其质量比活性和比表面比活性分别为商业化Pt/C催化剂的1.6和1.8倍。加速寿命实验表明,Pt/C@PANI(30%)催化剂具有很好的稳定性,经过1500圈CV扫描后,其电化学活性表面积仅下降了30%,而商业化Pt/C催化剂降低了83%。理论计算表明,PANI将电子转移给载体C,导致自身空穴增加,PANI部分氧化,导电性增强；PANI的存在使Pt/C@PANI体系的HOMO能级升高,减小了与氧气分子LUMO能级的差异,有利于电子从催化剂HOMO转移到氧分子的LUMO轨道,使得氧容易得到电子；PANI吸附后,Pt原子d带中心显著降低,利于中间物种的脱附,催化活性更高。结论 PANI包覆层抑制了Pt纳米粒子在载体表面的迁移、团聚长大和溶解/再沉积,有效地解决了Pt/C催化剂的Ostwald肿大,催化剂的活性和稳定性得到显著提升。
목적：제비일충구유고은정성화고최화활성적Pt/C@PANI“핵/각”결구최화제。방법이용원위화학양화취합법제비취분알수식Pt/C@PANI“핵/각”결구최화제,채용순배복안가속수명실험,결합전화학활성표면적、양환원활성、X-사선광전자능보화투사전경,고찰소제비최화제적활성화은정성,통과밀도범함이론탐구PANI증강Pt/C최화제활성화은정성적양자화학본질원인。결과전화학측시표명,Pt/C@PANI최화제적최화활성여취분알포복층함량화후도밀절상관,Pt/C@PANI(30%)최화제구유최호적최화활성,기질량비활성화비표면비활성분별위상업화Pt/C최화제적1.6화1.8배。가속수명실험표명,Pt/C@PANI(30%)최화제구유흔호적은정성,경과1500권CV소묘후,기전화학활성표면적부하강료30%,이상업화Pt/C최화제강저료83%。이론계산표명,PANI장전자전이급재체C,도치자신공혈증가,PANI부분양화,도전성증강；PANI적존재사Pt/C@PANI체계적HOMO능급승고,감소료여양기분자LUMO능급적차이,유리우전자종최화제HOMO전이도양분자적LUMO궤도,사득양용역득도전자；PANI흡부후,Pt원자d대중심현저강저,리우중간물충적탈부,최화활성경고。결론 PANI포복층억제료Pt납미입자재재체표면적천이、단취장대화용해/재침적,유효지해결료Pt/C최화제적Ostwald종대,최화제적활성화은정성득도현저제승。
ABSTRACT:Objective To prepare a Pt/C@PANI core-shell catalyst with high catalytic activity and durability. Methods The polyaniline ( PANI)-decorated Pt/C@PANI core-shell catalyst was prepared by in situ chemical oxidation polymerization method. The stability and activity of the Pt/C@PANI catalyst prepared were evaluated using accelerated durability test ( ADT) , along with the monitoring of electrochemical surface area (ECSA), oxygen reduction reaction (ORR) activities, X-ray photoelectron spec-trometer ( XPS) and transmission electron microscopy ( TEM) , and the density functional theory ( DFT) calculations were carried out to investigate the essential reasons for the enhanced catalytic activity and durability of Pt/C catalyst by PANI. Results The ex-perimental results demonstrated that the activity for the ORR strongly depended on the PANI content and the thickness of the PANI shell, and that the prepared Pt/C@PANI(30%) catalyst with 5 nm PANI exhibited a Pt mass and a specific activity of nearly 1. 6 and 1. 8 times higher than those of the commercial Pt/C catalysts. The accelerated stability test showed that the ECSA of Pt/C@PANI(30%) catalyst was only decreased by ~30%, whereas the Pt/C catalysts lost ~83% of the initial ECSA after 1500 cycles of CV scanning. The DFT calculations disclosed that the number of holes in PANI increased with the electrons transfer from PANI to the supporting C, which caused partial oxidation of PANI and thus strengthened the electric conductivity of PANI. The lifted HOMO energy level and lowered d band center of Pt/C@PANI compared with Pt/C were beneficial to the electron transfer between Pt/C@PANI and O2 due to the reduced gap between the Pt/C@PANI HOMO and the oxygen LUMO, and the desorption of inter-mediate species on the surface of the catalysts and releasing fresh catalytic sites for the subsequent reaction. Conclusion The PANI-decorated layer could enhance the Pt-support interaction and help to inhibit Pt dissolution/re-deposition, aggregation and rip-ening, which effectively solve the problem of Ostwald enlargement of the Pt/C catalyst, resulting in significant enhancement in the activity and stability of the catalyst.