Active and poisoning-resistant Ru-based electrocatalysts for the hydrogen oxidation reaction(HOR)are designed and fabricated by integrating Cu/Ru dual single atoms and alloy CuRu nanoparticles(N-(CuRu)_(NP+SA)@NC)thro...Active and poisoning-resistant Ru-based electrocatalysts for the hydrogen oxidation reaction(HOR)are designed and fabricated by integrating Cu/Ru dual single atoms and alloy CuRu nanoparticles(N-(CuRu)_(NP+SA)@NC)through a strategy involving weak chemical reduction and ammonia-assisted gas-phase nitridation.The resultant N-(CuRu)_(NP+SA)@NC electrocatalysts feature nitrogen atoms coordinated to both Cu and Ru metal atoms via strong N-metal interactions.Density functional theory calculations revealed that alloyed CuRu nanoparticles and monodispersed Cu atoms are vital for altering the electronic configuration of the host Ru elements.This finely tuned structure enhanced the adsorption of H and OH and promoted CO oxidation over the N-(CuRu)_(NP+SA)@NC electrocatalyst,resulting in high alkaline HOR activity,as evidenced by the higher exchange current density of 3.74 mA cm^(-2)and high mass activity of 3.28 mAμg_(Ru)^(-1),which are far superior to those of most Ru-based catalysts reported to date.Moreover,the N-(CuRu)_(NP+SA)@NC electrocatalysts are resistant to CO poisoning and can be used at a high concentration of 1000 ppm CO with no distinct decay in the activity,in stark contrast to the commercial Pt/C catalyst under the same conditions.展开更多
In addition to the electron transfer,the appropriate H-adsorption affinity of active centers on the metal cocatalyst surface is quite important for high hydrogen-production activity of cocatalyst-modified photo-cataly...In addition to the electron transfer,the appropriate H-adsorption affinity of active centers on the metal cocatalyst surface is quite important for high hydrogen-production activity of cocatalyst-modified photo-catalysts.The typical Cu and Ru metal cocatalysts clearly exhibit a weak Cu-H bond and a strong Ru-H bond,respectively,resulting in limited activity for photocatalytic H_(2)evolution.In this work,an ingenious strategy of self-optimized H-adsorption affinity in CuRu alloy cocatalyst is developed to simultaneously reinforce the Cu-H bond and weaken the Ru-H bond by the intrinsic electron transfer from Cu to Ru atom.The CuRu alloy nanoparticles(2-3 nm)were deposited on the TiO_(2)surface to prepare CuRu/TiO_(2)through a one-step photoreduction method.Photocatalytic tests exhibited that the highest H_(2)-production rate of CuRu/TiO_(2)photocatalyst reached up to 5.316 mmol h^(-1)g^(-1),which was 24.80,1.86,and 2.60 times higher than that of the TiO_(2),Cu/TiO_(2),and Ru/TiO_(2),respectively.Based on the characterization results and theoretical calculations,the CuRu alloy cocatalyst exhibits excellent self-optimized H-adsorption affinity via the spontaneous electron transfer from Cu to Ru atom,which can greatly accelerate the photocatalytic H_(2)-production rate of TiO_(2).This work provides a feasible idea for the self-optimized H-adsorption affinity of metal active sites in the photocatalytic H_(2)-generation field.展开更多
文摘Active and poisoning-resistant Ru-based electrocatalysts for the hydrogen oxidation reaction(HOR)are designed and fabricated by integrating Cu/Ru dual single atoms and alloy CuRu nanoparticles(N-(CuRu)_(NP+SA)@NC)through a strategy involving weak chemical reduction and ammonia-assisted gas-phase nitridation.The resultant N-(CuRu)_(NP+SA)@NC electrocatalysts feature nitrogen atoms coordinated to both Cu and Ru metal atoms via strong N-metal interactions.Density functional theory calculations revealed that alloyed CuRu nanoparticles and monodispersed Cu atoms are vital for altering the electronic configuration of the host Ru elements.This finely tuned structure enhanced the adsorption of H and OH and promoted CO oxidation over the N-(CuRu)_(NP+SA)@NC electrocatalyst,resulting in high alkaline HOR activity,as evidenced by the higher exchange current density of 3.74 mA cm^(-2)and high mass activity of 3.28 mAμg_(Ru)^(-1),which are far superior to those of most Ru-based catalysts reported to date.Moreover,the N-(CuRu)_(NP+SA)@NC electrocatalysts are resistant to CO poisoning and can be used at a high concentration of 1000 ppm CO with no distinct decay in the activity,in stark contrast to the commercial Pt/C catalyst under the same conditions.
基金supported by the National Natural Science Foun-dation of China(Nos.22178275 and U22A20147)the Natural Science Foundation of Hubei Province of China(No.2022CFA001).
文摘In addition to the electron transfer,the appropriate H-adsorption affinity of active centers on the metal cocatalyst surface is quite important for high hydrogen-production activity of cocatalyst-modified photo-catalysts.The typical Cu and Ru metal cocatalysts clearly exhibit a weak Cu-H bond and a strong Ru-H bond,respectively,resulting in limited activity for photocatalytic H_(2)evolution.In this work,an ingenious strategy of self-optimized H-adsorption affinity in CuRu alloy cocatalyst is developed to simultaneously reinforce the Cu-H bond and weaken the Ru-H bond by the intrinsic electron transfer from Cu to Ru atom.The CuRu alloy nanoparticles(2-3 nm)were deposited on the TiO_(2)surface to prepare CuRu/TiO_(2)through a one-step photoreduction method.Photocatalytic tests exhibited that the highest H_(2)-production rate of CuRu/TiO_(2)photocatalyst reached up to 5.316 mmol h^(-1)g^(-1),which was 24.80,1.86,and 2.60 times higher than that of the TiO_(2),Cu/TiO_(2),and Ru/TiO_(2),respectively.Based on the characterization results and theoretical calculations,the CuRu alloy cocatalyst exhibits excellent self-optimized H-adsorption affinity via the spontaneous electron transfer from Cu to Ru atom,which can greatly accelerate the photocatalytic H_(2)-production rate of TiO_(2).This work provides a feasible idea for the self-optimized H-adsorption affinity of metal active sites in the photocatalytic H_(2)-generation field.
