Optimizing Intermediate Adsorption over PdM (M=Fe, Co, Ni, Cu) Bimetallene for Boosted Nitrate Electroreduction to Ammonia

Yuanbo Zhou¹, Lifang Zhang⁴, Zebin Zhu¹, Mengfan Wang², Najun Li³, Tao Qian¹, Chenglin Yan^2.3.5*(晏成林), Jianmei Lu^1*(路建美)

¹CollaborativeInnovationCenterof SuzhouNanoScienceandTechnology,Collegeof ChemistryChemicalEngineeringandMaterialsScience,SoochowUniversity, 199 Ren’aiRoad,Suzhou215123,P. R. China

²Key Laboratoryof Core Technologyof HighSpecificEnergyBattery,CollegeofEnergy, SoochowUniversity, Suzhou

³Key Materialsfor Petroleumand ChemicalIndustry, CollegeofEnergy, SoochowUniversity, Suzhou

⁴Schoolof Chemistryand ChemicalEngineering,NantongUniversity, Nantong226019,P. R. China

⁵Schoolof PetrochemicalEngineering,ChangzhouUniversity,Changzhou213164,P. R. China

Angew. Chem.Int. Ed.2024,63,e202319029(1 of 9)

Abstract:Electrochemical reduction of nitrate to ammonia (NO₃RR) is a promising and eco-friendly strategy for ammonia production. However, the sluggish kinetics of the eight-electron transfer process and poor mechanistic understanding strongly impedes its application. To unveil the internal laws, herein, a library of Pd-based bimetallene with various transition metal dopants (PdM (M=Fe, Co, Ni, Cu)) are screened to learn their structure-activity relationship towards NO₃RR. The ultra-thin structure of metallene greatly facilitates the exposure of active sites, and the transition metals dopants break the electronic balance and upshift its d-band center, thus optimizing intermediates adsorption. The anisotropic electronic characteristics of these transition metals make the NO₃RR activity in the order of PdCu>PdCo approximate to PdFe>PdNi>Pd, and a record-high NH₃yield rate of 295 mg h^-1mg_cat^-1along with Faradaic efficiency of 90.9 % is achieved in neutral electrolyte on PdCu bimetallene. Detailed studies further reveal that the moderate N-species (*NO₃and *NO₂) adsorption ability, enhanced *NO activation, and reduced HER activity facilitate the NH3 production. We believe our results will give a systematic guidance to the future design of NO3RR catalysts.

链接：https://onlinelibrary.wiley.com/doi/10.1002/anie.202319029