Constructing efficient carbon material with enhanced mass transfer ability from vacuum residuum(VR)is of prime industrial and scientific significance.Herein,we demonstrated a one-pot synthesis of metal-free and highly...Constructing efficient carbon material with enhanced mass transfer ability from vacuum residuum(VR)is of prime industrial and scientific significance.Herein,we demonstrated a one-pot synthesis of metal-free and highly symmetric hollow carbon cubes(HCCs)using cost-efficient vacuum residuum(VR)as a C/N/S source.By multi-techniques such as TEM,SEM,Raman,XPS,and XRD,it is found that the CTAB surfactant plays an important role in emulsifying and forming oil-in-water suspension particles.Subsequently,high aromatics contents in VR favor the formation of HCCs shell by graphitization on the surface of Na Cl template.Notably,heavy metals(e.g.,V,Ni)are not enriched in carbon skeleton due to the unique graphitization mechanism.This metal-free HCCs catalyst showed good catalytic stability and high selectivity towards direct and local electrochemical production of hydrogen peroxide(H_(2)O_(2))through two-electron O_(2)reduction due to enhanced mass transfer ability.The results provide a novel avenue to synthesize metal-free cubic carbon material from low-cost and plentiful VR,which are essential to the design of more efficient catalysts for O_(2)reduction to H_(2)O_(2).展开更多
Rationally manipulating the in‐situ formed catalytically active surface of catalysts remains a great challenge for a highly efficient water electrolysis.Here,we report a cationic oxidation method which can adjust the...Rationally manipulating the in‐situ formed catalytically active surface of catalysts remains a great challenge for a highly efficient water electrolysis.Here,we report a cationic oxidation method which can adjust the leaching of the in‐situ catalyst and promote the reconstruction of dynamic surface for the oxygen evolution reaction(OER).The chlorine doping can reduce the possibility of triggering in‐situ cobalt oxidation and chlorine leaching,leading to a transformation of the surface chlorine doped LaCoO_(3)(Cl‐LaCoO_(3))into an intricate amorphous(oxygen)hydroxide phase.And thus,Cl‐LaCoO_(3)nanocrystals shows an ultralow overpotential of 342 mV at the current density of 10 mA cm^(–2)and Tafel slope of 76.2 mV dec–1.Surface reconstructed Cl‐LaCoO_(3)is better than many of the most advanced OER catalysts and has proven significant stability.This work provides a new prospect for designing a high‐efficiency electrocatalyst with optimized perovskite‐structure in renewable energy system.展开更多
The development of metal sulfide catalysts with remarkable activity toward efficient overall photocatalytic water splitting remains challenging owing to the dominant charge recombination and deficient catalytic active...The development of metal sulfide catalysts with remarkable activity toward efficient overall photocatalytic water splitting remains challenging owing to the dominant charge recombination and deficient catalytic active sites.Moreover,in the process of water oxidation catalysis,the inhibition of severe photocorrosion is an immense task,requiring effective photogenic hole-transfer kinetics.Herein,stratified Co-MnO_(2)@CdS/CoS hollow cubes with spatially separated catalytic sites were rationally designed and fabricated as highly efficient controllable catalysts for photocatalytic overall water splitting.The unique self-templated method,including a continuous anion/cation-exchange reaction,integrates a Co-doped oxidation co-catalyst(Co-MnO_(2))and a reduction co-catalyst(CoS)on the nanocubes with uniform interface contact and ultrathin two-dimensional(2D)nanometer sheets.We demonstrate that the stratified Co-MnO_(2)@CdS/CoS hollow cubes can provide an abundance of active sites for surface redox reactions and contribute to the separation and migration of the photoionization charge carriers.In particular,CoS nanoparticles dispersed on the walls of CdS hollow cubes were identified as reduction co-catalysts accelerating hydrogen generation,while Co-MnO_(2) nanosheets attached to the inner walls of the CdS hollow cube were oxidation co-catalysts,promoting oxygen evolution dynamics.Benefiting from the desirable structural and compositional advantages,optimized stratification of Co-MnO_(2)@CdS/CoS nanocubes provided a catalytic system devoid of precious metals,which exhibited a remarkable overall photocatalytic water-splitting rate(735.4(H_(2))and 361.1(O_(2))μmol h^(−1) g^(−1)),being among the highest values reported thus far for CdS-based catalysts.Moreover,an apparent quantum efficiency(AQE)of 1.32%was achieved for hydrogen evolution at 420 nm.This study emphasizes the importance of rational design on the structure and composition of photocatalysts for overall water splitting.展开更多
基金supported by the National Natural Science Foundation of China (21978325)。
文摘Constructing efficient carbon material with enhanced mass transfer ability from vacuum residuum(VR)is of prime industrial and scientific significance.Herein,we demonstrated a one-pot synthesis of metal-free and highly symmetric hollow carbon cubes(HCCs)using cost-efficient vacuum residuum(VR)as a C/N/S source.By multi-techniques such as TEM,SEM,Raman,XPS,and XRD,it is found that the CTAB surfactant plays an important role in emulsifying and forming oil-in-water suspension particles.Subsequently,high aromatics contents in VR favor the formation of HCCs shell by graphitization on the surface of Na Cl template.Notably,heavy metals(e.g.,V,Ni)are not enriched in carbon skeleton due to the unique graphitization mechanism.This metal-free HCCs catalyst showed good catalytic stability and high selectivity towards direct and local electrochemical production of hydrogen peroxide(H_(2)O_(2))through two-electron O_(2)reduction due to enhanced mass transfer ability.The results provide a novel avenue to synthesize metal-free cubic carbon material from low-cost and plentiful VR,which are essential to the design of more efficient catalysts for O_(2)reduction to H_(2)O_(2).
文摘Rationally manipulating the in‐situ formed catalytically active surface of catalysts remains a great challenge for a highly efficient water electrolysis.Here,we report a cationic oxidation method which can adjust the leaching of the in‐situ catalyst and promote the reconstruction of dynamic surface for the oxygen evolution reaction(OER).The chlorine doping can reduce the possibility of triggering in‐situ cobalt oxidation and chlorine leaching,leading to a transformation of the surface chlorine doped LaCoO_(3)(Cl‐LaCoO_(3))into an intricate amorphous(oxygen)hydroxide phase.And thus,Cl‐LaCoO_(3)nanocrystals shows an ultralow overpotential of 342 mV at the current density of 10 mA cm^(–2)and Tafel slope of 76.2 mV dec–1.Surface reconstructed Cl‐LaCoO_(3)is better than many of the most advanced OER catalysts and has proven significant stability.This work provides a new prospect for designing a high‐efficiency electrocatalyst with optimized perovskite‐structure in renewable energy system.
文摘The development of metal sulfide catalysts with remarkable activity toward efficient overall photocatalytic water splitting remains challenging owing to the dominant charge recombination and deficient catalytic active sites.Moreover,in the process of water oxidation catalysis,the inhibition of severe photocorrosion is an immense task,requiring effective photogenic hole-transfer kinetics.Herein,stratified Co-MnO_(2)@CdS/CoS hollow cubes with spatially separated catalytic sites were rationally designed and fabricated as highly efficient controllable catalysts for photocatalytic overall water splitting.The unique self-templated method,including a continuous anion/cation-exchange reaction,integrates a Co-doped oxidation co-catalyst(Co-MnO_(2))and a reduction co-catalyst(CoS)on the nanocubes with uniform interface contact and ultrathin two-dimensional(2D)nanometer sheets.We demonstrate that the stratified Co-MnO_(2)@CdS/CoS hollow cubes can provide an abundance of active sites for surface redox reactions and contribute to the separation and migration of the photoionization charge carriers.In particular,CoS nanoparticles dispersed on the walls of CdS hollow cubes were identified as reduction co-catalysts accelerating hydrogen generation,while Co-MnO_(2) nanosheets attached to the inner walls of the CdS hollow cube were oxidation co-catalysts,promoting oxygen evolution dynamics.Benefiting from the desirable structural and compositional advantages,optimized stratification of Co-MnO_(2)@CdS/CoS nanocubes provided a catalytic system devoid of precious metals,which exhibited a remarkable overall photocatalytic water-splitting rate(735.4(H_(2))and 361.1(O_(2))μmol h^(−1) g^(−1)),being among the highest values reported thus far for CdS-based catalysts.Moreover,an apparent quantum efficiency(AQE)of 1.32%was achieved for hydrogen evolution at 420 nm.This study emphasizes the importance of rational design on the structure and composition of photocatalysts for overall water splitting.
