ZIF-67-templated synthesis of core-shell-structured POP@MOF composite derived porous carbon with embedding FeCo alloy nanoparticles as high-performance bifunctional oxygen electrocatalysts
ZIF-67-templated synthesis of core-shell-structured POP@MOF composite derived porous carbon with embedding FeCo alloy nanoparticles as high-performance bifunctional oxygen electrocatalysts
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DOI：
10.1016/j.micromeso.2020.110627
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发表时间：
2020-11
影响因子：
5.2
通讯作者：
Meng Zhang;Fang Yan;Jingkun Bai;Xiaotong Li;Xiao-tong Zheng;Jinli Dou;Xuedong Wang;Weifen Zhang;Baolong Zhou
中科院分区：
文献类型：
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作者：
Meng Zhang;Fang Yan;Jingkun Bai;Xiaotong Li;Xiao-tong Zheng;Jinli Dou;Xuedong Wang;Weifen Zhang;Baolong Zhou
本论文采用一种合理有效的固相合成方法，以ZIF-67为模板剂，制备了铁基共轭微孔聚合物(Fe-phth-CMP)包覆金属有机骨架(ZIF-67)复合材料，即Fe-phth-CMP@ZIF-67。碳化后，这些特殊的复合材料具有与ZIF-67相似的可控形貌和可调的Fe/Co摩尔比，可以进一步转化为嵌入高度分散的FeCo合金和Fe/Co-N活性中心的N掺杂多孔炭。以mPOP：mZIF=2：3的质量比制备的最佳催化剂P2Z3-900具有层次化的孔结构，可显著提高传质效率，促进活性中心的暴露，同时在碱性条件下具有较高的ORR和OER活性。例如，P2Z3-900的半波电位(e1/2)为0.81nV(Vs RHE)，扩散限制电流密度为5.56mA/cm−2，与商用铂/碳(0.83nV和5.60mA/cm−2)相当，但远好于其他制备的对照样品。在10 mA/cm−2下的OER达到1.60V，小的塔菲尔斜率为57 mV/−1。更重要的是，目前的合成方法为结构、形态和元素组成可控的多孔炭提供了一种合理的策略，从而精细地调节了高效催化的性能。
Herein, Fe-phthalocyanine-based conjugated microporous polymer (Fe-Phth-CMP) coated metal organic framework (ZIF-67) composites, namely Fe-Phth-CMP@ZIF-67, were facilely prepared via a rational and effective solid-phase synthesis method, in which, ZIF-67 worked as both precursors and templates. Upon carbonization, these special composites, with controllable morphology similar to ZIF-67 and adjustable Fe/Co molar ratio, can be further converted into N-doped porous carbons embedded with highly dispersed FeCo alloy and Fe/Co–N active sites. The optimal catalyst (denoted as P2Z3-900, prepared in a mass ratio of mPOP: mZIF= 2 : 3) features hierarchical pore structure which could significantly enhance the mass transfer efficiency and promotes the exposure of active sites, leading to high ORR and OER activity in alkaline conditions, simultaneously. For example, P2Z3-900 presents a half-wave potential (E1/2) of 0.81 V (vs RHE) with a diffusion-limited current density of 5.56 mA cm−2, comparable to commercial Pt/C (0.83 V and 5.60 mA cm−2), but much better than other prepared control samples. TheEonsetof OER at 10 mA cm−2reaches 1.60 V with a small Tafel slope of 57 mV dec−1. More importantly, the current synthetic method offers a rational strategy to structure-, morphology-, and element composition-controlled porous carbons, thereby finely regulating the property for efficient catalysis.