Electrocatalytic reduction of NO(NORR) is an effective method for NH_(3) synthesis, due to low bonding energy of N–O bond. In this work, we have investigated many CrS_(2)based catalysts, including pristine CrS_(2),Cr...Electrocatalytic reduction of NO(NORR) is an effective method for NH_(3) synthesis, due to low bonding energy of N–O bond. In this work, we have investigated many CrS_(2)based catalysts, including pristine CrS_(2),CrS_(2)with one S vacancy(v-CrS_(2)), and Ti doped CrS_(2)(Ti@CrS_(2)). The results have shown that the pristine CrS_(2)exhibits inert character for NO activation. However, v-CrS_(2)and Ti@CrS_(2)can exhibit enhanced interaction with NO, due to increased charge transfer between NO and substrates(0.52–0.75 e) and enhanced adsorption energies of NO on the catalysts(-0.96~-1.64 e V), compared to the situation of CrS_(2)(0.065 e/-0.30 e V). From the free energy profiles of NO electro-reduction to NH3, we can see that the v-CrS_(2)and Ti@CrS_(2)all exhibit ultralow limiting potentials of-0.03~-0.47 V, following both*NOH and*NHO mechanisms. Therefore, introducing vacancy and doping are all promising modification strategies for NORR catalysts. The results have provided a new idea for the search of catalysts for efficient electrocatalytic reduction of NO.展开更多
基金funded by the Natural Science Foundation of China (No. 21603109)the Henan Joint Fund of the National Natural Science Foundation of China (No. U1404216)+1 种基金the Scientific Research Program Funded by Shaanxi Provincial Education Department (No. 20JK0676)supported by Natural Science Basic Research Program of Shanxi (Nos. 2022JQ-108, 2022JQ096)。
文摘Electrocatalytic reduction of NO(NORR) is an effective method for NH_(3) synthesis, due to low bonding energy of N–O bond. In this work, we have investigated many CrS_(2)based catalysts, including pristine CrS_(2),CrS_(2)with one S vacancy(v-CrS_(2)), and Ti doped CrS_(2)(Ti@CrS_(2)). The results have shown that the pristine CrS_(2)exhibits inert character for NO activation. However, v-CrS_(2)and Ti@CrS_(2)can exhibit enhanced interaction with NO, due to increased charge transfer between NO and substrates(0.52–0.75 e) and enhanced adsorption energies of NO on the catalysts(-0.96~-1.64 e V), compared to the situation of CrS_(2)(0.065 e/-0.30 e V). From the free energy profiles of NO electro-reduction to NH3, we can see that the v-CrS_(2)and Ti@CrS_(2)all exhibit ultralow limiting potentials of-0.03~-0.47 V, following both*NOH and*NHO mechanisms. Therefore, introducing vacancy and doping are all promising modification strategies for NORR catalysts. The results have provided a new idea for the search of catalysts for efficient electrocatalytic reduction of NO.
