Hydrogen evolution reaction(HER)in neutral medium suffers from slow kinetics as compared to that in alkaline or acidic conditions,owing to larger Ohmic loss and low proton concentration.Here we report that a self-supp...Hydrogen evolution reaction(HER)in neutral medium suffers from slow kinetics as compared to that in alkaline or acidic conditions,owing to larger Ohmic loss and low proton concentration.Here we report that a self-supported nanoporous Au-SnO_(x)(NP Au-SnO_(x))catalyst with gradient tin oxide surface could significantly enhance HER activity in neutral buffer solution(0.2 M PBS).The NP Au-SnO_(x)catalyst exhibits a low onset overpotential of 38 mV and a small Tafel slope of 79 mV dec^(−1).The current density of 10 mA cm^(−2)is manifested at an overpotential as low as 148 mV,representing the comparable performance of Pt/C catalyst.This high catalytic activity can retain at least 10 hours without any detectable decay.The superior HER activity is proposed to originate from the gradient SnO_(x)structure and metal/oxide interfaces in nanoporous ligaments.Furthermore,the X-ray photoelectron spectroscopy reveals that the gradient oxide in the ligament is remarkably stable during long-term reaction.展开更多
Electrochemical carbon dioxide reduction meditated by metallic catalysts suffers from restricted selectivity and competition from hydrogen evolution, which sensitively depends on ambiguous contributions of alloying an...Electrochemical carbon dioxide reduction meditated by metallic catalysts suffers from restricted selectivity and competition from hydrogen evolution, which sensitively depends on ambiguous contributions of alloying and strain state in bimetallic catalysts. Herein, nanoporous Au-Sn(NPAS) containing trace tin solute in Au lattices is delicately designed to convince real strain effect, while eliminating other undesirable factors, such as alloying, crystal facets and surface composition. Compared with nanoporous gold(NPG), the NPAS with a solute strain of ~2.2% enables more efficient CO2-to-CO conversion, with an efficiency as high as 92% at-0.85 V versus reversible hydrogen electrode(vs. RHE), and the high activity can retain for more than 8 h. The combination of HRTEM and surface valence band photoemission spectra reveals that the tensile strain on the surface of 3 D nanoporous structure promotes the catalytic activity by shifting up the d-band center and strengthening the adsorption of key intermediate *COOH. A small amount of Sn solute in the nanoporous alloy can prevent ligament coarsening effectively and improve the electrochemical stability.展开更多
基金financial support from the National Natural Science Foundation of China(51771078,91545131 and 51371084)China Postdoctoral Science Foundation(No.2017M612455).
文摘Hydrogen evolution reaction(HER)in neutral medium suffers from slow kinetics as compared to that in alkaline or acidic conditions,owing to larger Ohmic loss and low proton concentration.Here we report that a self-supported nanoporous Au-SnO_(x)(NP Au-SnO_(x))catalyst with gradient tin oxide surface could significantly enhance HER activity in neutral buffer solution(0.2 M PBS).The NP Au-SnO_(x)catalyst exhibits a low onset overpotential of 38 mV and a small Tafel slope of 79 mV dec^(−1).The current density of 10 mA cm^(−2)is manifested at an overpotential as low as 148 mV,representing the comparable performance of Pt/C catalyst.This high catalytic activity can retain at least 10 hours without any detectable decay.The superior HER activity is proposed to originate from the gradient SnO_(x)structure and metal/oxide interfaces in nanoporous ligaments.Furthermore,the X-ray photoelectron spectroscopy reveals that the gradient oxide in the ligament is remarkably stable during long-term reaction.
基金financial support from the National Natural Science Foundation of China(Nos.51771078,91545131 and 51371084)China Postdoctoral Science Foundation(No.2017M612455)。
文摘Electrochemical carbon dioxide reduction meditated by metallic catalysts suffers from restricted selectivity and competition from hydrogen evolution, which sensitively depends on ambiguous contributions of alloying and strain state in bimetallic catalysts. Herein, nanoporous Au-Sn(NPAS) containing trace tin solute in Au lattices is delicately designed to convince real strain effect, while eliminating other undesirable factors, such as alloying, crystal facets and surface composition. Compared with nanoporous gold(NPG), the NPAS with a solute strain of ~2.2% enables more efficient CO2-to-CO conversion, with an efficiency as high as 92% at-0.85 V versus reversible hydrogen electrode(vs. RHE), and the high activity can retain for more than 8 h. The combination of HRTEM and surface valence band photoemission spectra reveals that the tensile strain on the surface of 3 D nanoporous structure promotes the catalytic activity by shifting up the d-band center and strengthening the adsorption of key intermediate *COOH. A small amount of Sn solute in the nanoporous alloy can prevent ligament coarsening effectively and improve the electrochemical stability.
