Graphdiyne-Supported Single-Atom-Sized Fe Catalysts for the Oxygen Reduction Reaction: DFT Predictions and Experimental Validations
Gao, Y (Gao, Yuan)[ 1 ] ; Cai, ZW (Cai, Zhewei)[ 2 ] ; Wu, XC (Wu, Xingchen)[ 1 ] ; Lv, ZL (Lv, Zhilie)[ 1 ] ; Wu, P (Wu, Ping)[ 1 ]*（吴萍）; Cai, CX (Cai, Chenxin)[ 1 ]*（蔡称心）

[ 1 ] Nanjing Normal Univ, Coll Chem & Mat Sci, Jiangsu Collaborat Innovat Ctr Biomed Funct Mat, Jiangsu Key Lab New Power Batteries, Nanjing 210097, Jiangsu, Peoples R China
[ 2 ] Clarkson Univ, Dept Chem & Biomol Engn, Potsdam, NY 13699 USA

ACS CATALYSIS，201811,8(11),10364-10374

Single-atom-sized catalysts (often called single atom catalysts) are highly desired for maximizing the efficiency of metal atom use. However, their synthesis is a major challenge that largely depends on finding an appropriate supporting substrate to achieve a well-defined and highly dispersed single atom. This work demonstrates, based on density functional theory (DFT) predictions and experimental validations, that graphdiyne is a good substrate for anchoring Fe atoms through the formation of covalent Fe-C bonds to produce graphdiyne-supported single-atom-sized Fe catalysts (Fe-graphdiyne catalysts); moreover, this catalyst shows high catalytic activity to oxygen reduction reactions (ORRs) similar to or even slightly better than the precious metal benchmark (commercial 20 wt % Pt/C catalyst). DFT predicts that the O-2 molecule can bind with an Fe atom, and the electron transformation process of ORRs occurs through a 4e(-) pathway. To validate the theoretical predictions, the Fe-graphdiyne catalyst was then synthesized by a reduction of Fe3+ ions adsorbed on a graphdiyne surface in aqueous solution, and its electrocatalytic activities toward ORR were experimentally evaluated in alkaline electrolytes (0.1 M KOH). The electrochemical measurements indicate that the Fe-graphdiyne catalyst can facilitate the 4e(-) ORR while limiting the 2e(-) transfer reaction, showing a high 4e(-) selectivity for ORRs and a good agreement with DFT predictions. The results presented here demonstrate that graphdiyne can provide a unique platform for synthesizing well-defined and uniform single-atom-sized metal catalysts with high catalytic activity toward ORRs.

文章链接： 
https://pubs.acs.org/doi/10.1021/acscatal.8b02360

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