The rational design and construction of inexpensive and highly active electrocatalysts for hydrogen evolution reaction(HER)is of great importance for water splitting.Herein,we develop a facile approach for preparation...The rational design and construction of inexpensive and highly active electrocatalysts for hydrogen evolution reaction(HER)is of great importance for water splitting.Herein,we develop a facile approach for preparation of porous carbon-confined Ru-doped Cu nanoparticles(denoted as Ru-Cu@C)by direct pyrolysis of the Ru-exchanged Cu-BTC metal–organic framework.When served as the electrocatalyst for HER,strikingly,the obtained Ru-Cu@C catalyst exhibits an ultralow overpotential(only 20 mV at 10 mA cm^(-2))with a small Tafel slope of 37 m V dec^(-1)in alkaline electrolyte.The excellent performance is comparable or even superior to that of commercial Pt/C catalyst.Density functional theory(DFT)calculations confirm that introducing Ru atoms into Cu nanocrystals can significantly alter the desorption of H_(2) to achieve a close-to-zero hydrogen adsorption energy and thereby boost the HER process.This strategy gives a fresh impetus to explore low-cost and high-performance catalysts for HER in alkaline media.展开更多
The development of a non-precious metal electrocatalyst （NPME） with a performance superior to commercial Pt/C for the oxygen reduction reaction （ORR） is important for the commercialization of fuel cells. We report...The development of a non-precious metal electrocatalyst （NPME） with a performance superior to commercial Pt/C for the oxygen reduction reaction （ORR） is important for the commercialization of fuel cells. We report the synthesis of a NPME by heat-treating Co-based metal organic frameworks （ZIF-67） with a small average size of 44 nm. The electrocatalyst pyrolyzed at 600 ~C showed the best performance and the performance was enhanced when it was supported on BP 2000. The resulting electrocatalyst was composed of 10 nm Co nanoparticles coated by 3-12 layers of N doped graphite layers which as a whole was embedded in a carbon matrix. The ORR performance of the electrocatalyst was tested by rotating disk electrode tests in O2-saturated 0.1 mol/L KOH under ambient conditions. The electrocatalyst （1.0 mg/cm~] showed an onset potential of 1.017 V （[vs. RHE] and a half-wave potential of 0.857 V （vs. RHE], which showed it was as good as the commer- cial Pt/C （20 BgPt/cm2）. Furthermore, the electrocatalyst possessed much better stability and re- sistance to methanol crossover than Pt/C.展开更多
Developing highly efficient,cost-effective,and stable electrocatalysts for hydrogen evolution reaction(HER)is of considerable importance but remains challenging.Herein,we report the fabrication of a robust Ru-based el...Developing highly efficient,cost-effective,and stable electrocatalysts for hydrogen evolution reaction(HER)is of considerable importance but remains challenging.Herein,we report the fabrication of a robust Ru-based electrocatalyst,which comprises heterostructured Ru-Ru_(2)P nanoparticles that are embedded in the N,P-codoped carbon nanofibers(CNFs),through a synthetic strategy involving electrospinning and temperature-controlled pyrolysis treatment.The as-prepared Ru-Ru_(2)P catalyst(Ru-Ru_(2)P@CNFs)shows excellent HER catalytic activities with low overpotentials of 11 and 14 mV in acidic and alkaline media,respectively,to achieve a current density of 10 mA cm^(−2),which are superior to the individual components of pure Ru and Ru_(2)P catalysts.Density functional theory calculations demonstrate the existence of electronic coupling effect between Ru and Ru_(2)P at the heterointerfaces,leading to a well-modulated electronic structure with optimized hydrogen adsorption strength and enhanced electrical conductivity for efficient HER electrocatalysis.In addition,the overall synthetic strategy can be generalized for the synthesis of a series of transitional metal phosphide-based nanofibers,thereby holding a remarkable capacity for various potential applications.展开更多
基金the National Key R&D Program of China(2018YFB0605700)the National Natural Science Foundation of China(51778570,51879230,21725101,21871244,21521001,and 21703145)+1 种基金China Postdoctoral Science Foundation(2019TQ0298,2019M660151)Fujian Institute of Innovation(CAS)。
文摘The rational design and construction of inexpensive and highly active electrocatalysts for hydrogen evolution reaction(HER)is of great importance for water splitting.Herein,we develop a facile approach for preparation of porous carbon-confined Ru-doped Cu nanoparticles(denoted as Ru-Cu@C)by direct pyrolysis of the Ru-exchanged Cu-BTC metal–organic framework.When served as the electrocatalyst for HER,strikingly,the obtained Ru-Cu@C catalyst exhibits an ultralow overpotential(only 20 mV at 10 mA cm^(-2))with a small Tafel slope of 37 m V dec^(-1)in alkaline electrolyte.The excellent performance is comparable or even superior to that of commercial Pt/C catalyst.Density functional theory(DFT)calculations confirm that introducing Ru atoms into Cu nanocrystals can significantly alter the desorption of H_(2) to achieve a close-to-zero hydrogen adsorption energy and thereby boost the HER process.This strategy gives a fresh impetus to explore low-cost and high-performance catalysts for HER in alkaline media.
基金supported by the National Basic Research Program of China(973 Program,2015CB932304)the National Natural Science Founda-tion of China(21436003)
文摘The development of a non-precious metal electrocatalyst （NPME） with a performance superior to commercial Pt/C for the oxygen reduction reaction （ORR） is important for the commercialization of fuel cells. We report the synthesis of a NPME by heat-treating Co-based metal organic frameworks （ZIF-67） with a small average size of 44 nm. The electrocatalyst pyrolyzed at 600 ~C showed the best performance and the performance was enhanced when it was supported on BP 2000. The resulting electrocatalyst was composed of 10 nm Co nanoparticles coated by 3-12 layers of N doped graphite layers which as a whole was embedded in a carbon matrix. The ORR performance of the electrocatalyst was tested by rotating disk electrode tests in O2-saturated 0.1 mol/L KOH under ambient conditions. The electrocatalyst （1.0 mg/cm~] showed an onset potential of 1.017 V （[vs. RHE] and a half-wave potential of 0.857 V （vs. RHE], which showed it was as good as the commer- cial Pt/C （20 BgPt/cm2）. Furthermore, the electrocatalyst possessed much better stability and re- sistance to methanol crossover than Pt/C.
基金financially supported by the Natural Science Foundation of Zhejiang Province (LQ20B030001 and LY20E020002)China Postdoctoral Science Foundation (2021M702305)。
文摘Developing highly efficient,cost-effective,and stable electrocatalysts for hydrogen evolution reaction(HER)is of considerable importance but remains challenging.Herein,we report the fabrication of a robust Ru-based electrocatalyst,which comprises heterostructured Ru-Ru_(2)P nanoparticles that are embedded in the N,P-codoped carbon nanofibers(CNFs),through a synthetic strategy involving electrospinning and temperature-controlled pyrolysis treatment.The as-prepared Ru-Ru_(2)P catalyst(Ru-Ru_(2)P@CNFs)shows excellent HER catalytic activities with low overpotentials of 11 and 14 mV in acidic and alkaline media,respectively,to achieve a current density of 10 mA cm^(−2),which are superior to the individual components of pure Ru and Ru_(2)P catalysts.Density functional theory calculations demonstrate the existence of electronic coupling effect between Ru and Ru_(2)P at the heterointerfaces,leading to a well-modulated electronic structure with optimized hydrogen adsorption strength and enhanced electrical conductivity for efficient HER electrocatalysis.In addition,the overall synthetic strategy can be generalized for the synthesis of a series of transitional metal phosphide-based nanofibers,thereby holding a remarkable capacity for various potential applications.
