Surface-supported isolated atoms in single-atom catalysts(SACs)grant maximum utilization of metals in heterogeneous catalysis.Herein,we report a feasible pyrolysis strategy to synthesize Pd single atoms by thermally m...Surface-supported isolated atoms in single-atom catalysts(SACs)grant maximum utilization of metals in heterogeneous catalysis.Herein,we report a feasible pyrolysis strategy to synthesize Pd single atoms by thermally melting Pd nanoparticles on an oxygen-vacancy-rich tungsten-oxide matrix at reduction atmosphere.Near ambient pressure X-ray photoelectron spectroscopy was used to monitor the formation of zero-valence Pd single atoms and the increased metallic feature of WO_(3-x)substrate.Accordingly,the as-obtained zero-valence Pd single-atom catalyst exhibits a markedly boosted HER activity with a low overpotential(η_(10)=70 mV)at the current density of 10 mA/cm2and a small Tafel slope(b=68 mV/dec),nearly 150 mV and a 3,0-fold enhancement than those of Pd nanoparticles(η_(10)=220 mV,b=133 mV/dec)under the same conditions.In addition,quasi in situ XPS results suggest the hydrogen spillover effect is more likely to occur on Pd single atoms during the electrochemical process.Our work may pave an interesting route for the rational design of highly-efficient single-atom catalysts,and the elucidation of corresponding enhanced reaction mechanisms by the utilization of advanced characterization techniques.展开更多
基金the support from the National Key R&D Program of China(No.2022YFA1503801)the National Natural Science Foundation of China(No.22172190,No.22202232 and No.22109171)。
文摘Surface-supported isolated atoms in single-atom catalysts(SACs)grant maximum utilization of metals in heterogeneous catalysis.Herein,we report a feasible pyrolysis strategy to synthesize Pd single atoms by thermally melting Pd nanoparticles on an oxygen-vacancy-rich tungsten-oxide matrix at reduction atmosphere.Near ambient pressure X-ray photoelectron spectroscopy was used to monitor the formation of zero-valence Pd single atoms and the increased metallic feature of WO_(3-x)substrate.Accordingly,the as-obtained zero-valence Pd single-atom catalyst exhibits a markedly boosted HER activity with a low overpotential(η_(10)=70 mV)at the current density of 10 mA/cm2and a small Tafel slope(b=68 mV/dec),nearly 150 mV and a 3,0-fold enhancement than those of Pd nanoparticles(η_(10)=220 mV,b=133 mV/dec)under the same conditions.In addition,quasi in situ XPS results suggest the hydrogen spillover effect is more likely to occur on Pd single atoms during the electrochemical process.Our work may pave an interesting route for the rational design of highly-efficient single-atom catalysts,and the elucidation of corresponding enhanced reaction mechanisms by the utilization of advanced characterization techniques.
