Enhanced nitrite electroreduction to ammonia via interfacial dual-site adsorption  

作　　者：Xiaokang Chen Shengliang Zhai Yi Tan Le Su Dong Zhai Wei-Qiao Deng Hao Wu 

机构地区：[1]Institute of Frontier Chemistry,School of Chemistry and Chemical Engineering,Shandong University,Qingdao 266071,Shandong,China [2]College of Physics and Information Engineering,Shanxi Normal University,Taiyuan 030031,Shanxi,China [3]Suzhou Research Institute of Shandong University,Suzhou 215123,Jiangsu,China

出　　处：《Journal of Energy Chemistry》2024年第9期328-335,共8页能源化学（英文版）

基　　金：supported by the National Key R&D Program of China(Nos.2022YFA1503104 and 2022YFA1503102);the Natural Science Foundation of Shandong Province(No.2022HWYQ-009);the Natural Science Foundation of Jiangsu Province(No.BK20230243);Taishan Scholars Project(No.tspd20230601);Qilu Young Scholars Program of Shandong University.

摘　　要：The nitrite(NO_(2)^(−))to ammonia(NH3)electroreduction reaction(NO_(2)^(−)RR)would be impeded by sluggish proton-coupled electron transfer kinetics and competitive hydrogen evolution reaction(HER).A key to improving the NH_(3) selectivity is to facilitate adsorption and activation of NO_(2)^(−),which is generally undesirable in unitary species.In this work,an efficient NO_(2)^(−)RR catalyst is constructed by cooperating Pd with In2O3,in which NO_(2)^(−)could adsorb on interfacial dual-site through“Pd–N–O–In”linkage,leading to strengthened NO_(2)^(−)adsorption and easier N=O bond cleavage than that on unitary Pd or In2O3.Moreover,the Pd/In_(2)O_(3)composite exhibits moderate H^(*)adsorption,which may facilitate protonation kinetics while inhibiting competitive HER.As a result,it exhibits a fairly high NH_(3)yield rate of 622.76 mmol h^(−1)g^(−1)cat with a Faradaic efficiency(FE)of 95.72%,good selectivity of 91.96%,and cycling stability towards the NO_(2)^(−)RR,surpassing unitary In_(2)O_(3)and Pd/C electrocatalysts.Besides,computed results indicate that NH_(3)production on Pd/In_(2)O_(3)follows the deoxidation to hydrogenation pathway.This work highlights the significance of H^(*)and NO_(2)^(−)adsorption modulation and N=O activation in NO_(2)^(−)RR electrochemistry by creating synergy between a mediocre catalyst with an appropriate cooperator.

关 键 词：Dual-site adsorption Nitrite electroreduction AMMONIA Pd Hydrogenation 

分 类 号：TQ113.2[化学工程—无机化工] O643.36[理学—物理化学]