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学校地址:辽宁省大连市甘井子区凌工路2号
实验室地址:大连理工大学三束实验室4号楼
氧还原无铂催化剂

基于动力学缓慢氧还原反应,针对铂基催化剂成本高、循环稳定性差等关键问题,团队致力于研发低成本、高活性无铂催化剂。以材料结构设计和活性位点构建为主导,利用热丝气相沉积、静电纺丝、高温热解、热弧等离子体等方法调控制备不同体系无铂催化剂,分析微观结构、内在活性与催化性能的内在联系,深入探索催化机制等关键科学问题,为高性能无铂催化剂提供新策略。

单原子催化剂结构均一、金属原子利用效率可实现最大化、具有独特的高活性;本团队采用直流电弧物理法制备的Nb单原子镶嵌石墨纳米结构,因其d-轨道电子重构,拥有比贵金属更优异的氧还原反应催化能力。在长效服役过程中,该纳米结构体现出突出的催化稳定性。杂原子掺杂碳材料因具有高催化活性、良好的稳定性和甲醇耐受性而备受关注;利用热丝化学气相沉积制备的不同碳基材料,杂原子掺入改变了碳材料的电子结构,表现出较好的催化稳定性。对于性能优异的氮掺杂碳体系,吡啶氮和石墨氮被认为是有效的活性位点;首次提出利用静电纺丝与熔盐辅助相配合,设计开发富含氮掺杂一维交联介孔碳基催化剂,超高表面积(1069 m2/g)极大地提高了传质性能和活性位点的数量,表现出卓越的催化活性(E1/2=0.79 V)。氮掺杂碳负载过渡金属(M‑N‑C)催化剂,尤其是Fe‑N‑C具有高活性和高稳定性,是最具前景的Pt/C替代品之一。介于单原子Fe-NX活性位点和纳米粒子协同促进ORR反应速率;本团队在铁基催化剂中引入稀土铈,制备了一种N-CNTs高负载金属催化剂(Fe/Ce-NCNTs)。合成的Fe/Ce-NCNTs催化剂富含多种活性位点,在碱性介质中展示出优异的ORR性能(E1/2=0.86 V),在金属铝空气燃料电池应用中具有良好的电化学性能。

图2.jpg

1. (A-C)Nb单原子镶嵌石墨纳米结构[1],(D)富氮掺杂一维交联介孔碳基催化剂[7],(E)N-CNTs高负载金属催化剂[8]

代表性成果:

[1]. Zhang XF, Guo JJ, Guan PF, Liu CJ, Huang H, Xue FH, Dong XL*, Pennycook S, Chisholm MF*, Catalytically active single-atom niobium in graphitic layers, Nature Communications, 2013, 4: 1924.

[2].  Suo N, Wu AM, Huang H, Cao GZ, Zhang GF*, Electrocatalytic oxygen reduction reaction activity of KOH etched carbon films as metal-free cathodic catalysts for fuel cells, RSC Advances, 2019, 9: 2803-2811.

[3].  Wang CS, Suo N, Wu AM, Huang H, Cao GZ, Zhang GF*, Effect of oxidizing treatment on electrocatalytic activity of boron-doped amorphous carbon thin films, Carbon Letters, 2019, 29: 487-495.

[4].  Suo N, Huang H, Wu AMCao GZ, Zhang GF*, A novel method of synthesizing boron-doped carbon catalysts, Fuel Cells, 2018, 18: 681-687.

[5]. Suo N, Huang H, Wu AM, Cao GZ, Zhang GF*, Porous boron doped diamonds as metal-free catalysts for the oxygen reduction reaction in alkaline solution, Applied Surface Science, 2018, 439: 329-335.

[6]. Suo N, Huang H, Wu AM, Cao GZ, Zhang GF*, Effect of methane concentration on oxygen reduction reaction of carbon films in alkaline solution, International Journal of Hydrogen Energy, 2018, 43: 18194-18201.

[7]. Ran S, Qi J*, Dong XF, Huang H*, Qi M, Dong WJ, Zhao PH, Zhao ZH, Yang JY. Molten NaCl assisted pyrolysis of ZIF-8/PAN electrospun fibers to synthesis 1D cross-linked mesoporous N-rich carbon as oxygen reduction electrocatalysts, Chemical Engineering Journal, 2023, 463: 142174.

[8]Wang J, Wu AM*, Qiu ZW, Qin WJ, Li AK, Huang H. N-CNT supported Fe/Ce bimetallic catalyst for Al-air aqueous batteries, Applied Surface Science, 2023, 608: 155185.