原位电化学钾离子插层促进层间限域的硝酸盐还原制氨反应  

Boosting the interlayer-confined nitrate reduction reaction by in situ electrochemical potassium ion intercalation

作　　者：徐梦秋 章烨 周海桥 李笑宇 周钰虎 徐旭东 贾淦 祝根平 毋芳芳 高鹏 叶伟 Mengqiu Xu;Ye Zhang;Haiqiao Zhou;Xiaoyu Li;Yuhu Zhou;Xudong Xu;Gan Jia;Genping Zhu;Fangfang Wu;Peng Gao;Wei Ye(College of Material,Chemistry and Chemical Engineering,Key Laboratory of Organosilicon Chemistry and Material Technology,Ministry of Education,Hangzhou Normal University,Hangzhou 311121,China;College of Materials Science and Engineering,Zhejiang University of Technology,Hangzhou 310014,China)

机构地区：[1]College of Material,Chemistry and Chemical Engineering,Key Laboratory of Organosilicon Chemistry and Material Technology,Ministry of Education,Hangzhou Normal University,Hangzhou 311121,China [2]College of Materials Science and Engineering,Zhejiang University of Technology,Hangzhou 310014,China

出　　处：《Science China Materials》2023年第4期1352-1361,共10页中国科学（材料科学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(51902077 and 22005268);Zhejiang Provincial Natural Science Foundation(LQ19B010001);Zhejiang Province"Ten Thousand People Plan";Innovation and Entrepreneurship Project of High-Level Overseas Students in Hangzhou in 2021;the Research StartUp Fund of Hangzhou Normal University(4095C5021920466)。

摘　　要：将硝酸根离子电化学转化回有价值的氨(NH_(3))是传统Haber Bosch工艺的一种可能的替代方案.然而,硝酸根电还原制氨目前仍然受制于从NO_(3)^(-)到NH_(3)的低催化活性和低法拉第效率(FE).本文中,我们报告了二维层状结构中的层间限域的硝酸盐还原制氨反应(NTRR).结果表明,原位电化学钾离子(K^(+))插层扩大了层间距,从而触发了层间限域的NTRR.所制备的α-Ni_(0.902)Cu_(0.098)(OH)_(2)超薄纳米片具有高的NTRR性能,在-0.6 V(相对于可逆氢电极)下的NH_(3)产率和FE分别达到了13.4 mol g_(cat).^(-1)h^(-1)和98.9%,远超过已报道的铜基电催化剂.此外,该催化剂还表现出良好的循环稳定性,连续循环20次后活性和FE没有明显的衰减.此外,我们利用原位电化学拉曼光谱结果揭示了从NO_(3)^(-)到NH_(3)的途径.Electrochemically converting nitrate ions back to valuable ammonia(NH_(3))represents a sustainable alternative to the traditional Haber-Bosch process.However,NH_(3)electrosynthesis is currently restricted by the low catalytic activities and Faradaic efficiency(FE)of NO_(3)^(-)-to-NH_(3).Here we report an interlayer-confined nitrate reduction reaction(NTRR)in a two-dimensional layered structure.The results indicate that in situ electrochemical K^(+)intercalation expands the interlayer spacing,which triggers the NTRR between layers.The obtainedα-Ni_(0.902)Cu_(0.098)(OH)_(2)ultrathin nanosheets deliver high NTRR performance with an NH_(3)yield rate of 13.4 mol g_(cat).^(-1)h^(-1)and NO_(3)^(-)-to-NH_(3)FE of 98.9%at-0.6 V,far exceeding those of Cu-based electrocatalysts.Moreover,the catalyst exhibits good cycling stability,which can sustain 20 successive cycles without obvious decay of activity and NH_(3)FE.Meanwhile,in situ electrochemical Raman spectroscopy results unravel the NO_(3)^(-)-to-NH_(3)pathway.

关 键 词：拉曼光谱 电还原 硝酸根 电催化剂 连续循环 制氨 氢电极 替代方案 

分 类 号：TQ113.26[化学工程—无机化工] TQ426