碳布负载的高分散CoP_(x)纳米粒子及其甲醇电催化氧化反应性能的研究  

Highly dispersed CoP_(x)nanoparticles supported on carbon cloth for the enhanced catalytic performance of methanol electro-oxidation

作　　者：张见远 邢双凤 赵世超[1] 熊咪 张变琴 童希立[1] 覃勇[1] 高哲[1] ZHANG Jian-yuan;XING Shuang-feng;ZHAO Shi-chao;XIONG Mi;ZHANG Bian-qin;TONG Xi-li;QIN Yong;GAO Zhe(State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China;Center of Materials Science and Optoelectronics Engineering,University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院山西煤炭化学研究所煤转化国家重点实验室,山西太原030001 [2]中国科学院大学材料与光电研究中心,北京100049

出　　处：《燃料化学学报》2022年第10期1270-1277,共8页Journal of Fuel Chemistry and Technology

基　　金：supported by the National Key R&D Program of China(2020YFA0210902 and 2017YFA0700101);National Natural Science Foundation of China(U1932131 and U1832208);National Science Fund for Distinguished Young Scholars(21825204);Youth Innovation Promotion Association of the Chinese Academy of Sciences(2018208)。

摘　　要：直接甲醇燃料电池(DMFC)是一种有潜力的商用燃料电池技术,目前贵金属阳极材料昂贵的价格阻碍其发展。开发分散均匀粒径分布窄的金属磷化物催化剂仍然是一个挑战。本研究通过原子层沉积法(ALD)在碳布上沉积CoO_(x),然后经过磷化处理获得CoP_(x)。通过改变ALD臭氧脉冲(ALD-O_(3))的循环数,调控CoO_(x)(ALD-CoO_(x))在碳布上的成核生长方式,获得粒径小、分布均匀的CoP_(x)纳米粒子。经过优化后的CoP_(x)纳米催化剂(CoP_(x)/40-CC)在碱性溶液中对甲醇电催化氧化反应表现出优异的活性(153 mA/cm^(2)),高于浸渍法制备的催化剂(Imp-CoP_(x)/CC),尽管CoP_(x)/40-CC的CoP_(x)负载量低于Imp-CoP_(x)/CC。结果表明,甲醇电催化氧化过程中的电子转移和传质动力学得到了提高,这得益于CoP_(x)较小的粒径和均匀的分布。Direct methanol fuel cell(DMFC)is a potential commercial fuel cell technology that is presently hindered by the expensive noble metal materials of the anode.Developing a method to obtain a uniformly dispersed metal phosphide catalyst with narrow size distribution is still a challenge.In this work,cobalt oxide was deposited on carbon cloth(CC)through atomic layer deposition(ALD),then cobalt phosphide was obtained after the phosphorization process.By changing the number of ALD-based ozone pulses(ALD-O_(3)) for CC,the nucleation and growth modes of cobalt oxide(ALD-CoO_(x))on the CC were regulated,and CoP_(x) nanoparticles with small particle size and uniform distribution were obtained.The optimized CoP_(x)-based catalyst with 40 cycles of ALD-O_(3) treatment(CoP_(x)/40-CC)exhibits excellent activity(153 mA/cm^(2)) toward methanol electrocatalytic oxidation reaction in the alkaline solution,which is higher than the catalyst prepared by impregnation(ImpCoP_(x)/CC),although the CoP_(x) loading of CoP_(x)/40-CC is lower than that of Imp-CoP_(x)/CC.The results indicate that the enhanced activity benefits from the small particle size and the uniform CoP_(x) distribution,which promote the electron-transfer and mass transport kinetics of the methanol electro-oxidation process.

关 键 词：原子层沉积 磷化钴纳米粒子 甲醇电催化氧化 

分 类 号：O643.3[理学—物理化学]