Transition metal phosphides are considered ideal alternatives for noble metal catalysts in hydrogen evolution reactions.In this study,amorphous NiCuFeP nanosheets were uniformly coated on self-supporting Cu_(3)P nanow...Transition metal phosphides are considered ideal alternatives for noble metal catalysts in hydrogen evolution reactions.In this study,amorphous NiCuFeP nanosheets were uniformly coated on self-supporting Cu_(3)P nanowire arrays through a facile electrodeposition method.The obtained_(3)D hierarchical NiCuFeP@Cu_(3)P/CF with good conductivity and abundant active sites was used as a hydrogen evolution reaction electrocatalyst.There are strong electronic interactions between each component of the material,as well as between the metal elements and P,which are conducive to improving the catalytic performance.展开更多
Electrocatalytic conversion presents a promising alternative to conventional industrial catalysis.While aqueous-phase electrocatalysis has achieved notable advancements,oil-water immiscible systems remain challenging ...Electrocatalytic conversion presents a promising alternative to conventional industrial catalysis.While aqueous-phase electrocatalysis has achieved notable advancements,oil-water immiscible systems remain challenging due to restricted reaction flux at multiphase interfaces.To address the limitation,we engineered a biphasic reaction system featuring a tailored oil-water catalytic interface in cyclohexene oxidation reaction(COR).The system employed a catalyst-loaded porous electrode as an active phase domain,enabling spatial separation of cyclohexene(organic phase)and electrolyte(aqueous phase).The tailored oil-water interface enhanced the interfacial mass transfer of substrate-catalysts and facilitated the spontaneous migration of 2-cyclohexen-1-ol into the aqueous phase,thereby streamlining product separation.Notably,polyaniline(PANI)modification on Co_(3)O_(4)enhanced surface lipophilicity,promoting cyclohexene adsorption and accelerating the COR catalytic kinetics(Co^(3+)-O+cyclohexene-H+e-→Co^(2+)-OH+2-cyclohexen-1-ol).The synergistic effects of optimized interfacial engineering and catalyst functionalization achieved exceptional performance:a current density of 45 mA·cm^(-2)at 1.6 V vs.reversible hydrogen electrode(V_(RHE)),coupled with 96.2%selectivity and 82.9%Faradaic efficiency.This work establishes an innovative paradigm for electrocatalytic conversions in oil-water immiscible systems through rational interface design and catalyst surface modulation.展开更多
Regulating the crystal plane exposure of catalysts is an effective way of enhancing their oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)activities.Herein,we have synthesized ultrathin metal phosphi...Regulating the crystal plane exposure of catalysts is an effective way of enhancing their oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)activities.Herein,we have synthesized ultrathin metal phosphide(NiFeCuP)nanosheets via the topotactic transformation of layered double hydroxide(LDH)precursors,based on their tunable composition and special layered structure.These as-prepared metal phosphides not only inherit the ultrathin nanosheet structure of LDHs,but also maintain metal atomic dispersion of the LDH precursors,thus exposing more active sites and increasing their internal activity.Moreover,the presence of the heteroatomic Cu atom in ultrathin NiFeCuP nanosheets regulates the exposed crystal plane,that is,it induces the(210)crystal plane exposure and tunes the electronic structure to enhance OER and HER performances.Experiments combined with calculations indicate that ultrathin NiFeCuP nanosheets with surface reconstruction and regulated electronic structures optimize the ΔG value of the intermediates during the water splitting process,thereby exhibiting obviously improved HER and OER performances,and excellent overall water splitting activity.The prepared bi-functional catalyst exhibits an HER overpotential of 86 mV and an OER overpotential of 156 mV at 10 mA cm−2.This results in a low cell voltage of only 1.49 V to drive the overall water splitting in alkaline solutions.This work provides a new idea for the development of bi-functional catalysts exhibiting excellent performances by regulating the exposed crystal plane.展开更多
基金supported by the National Natural Science Foundation of China(no.2177060378 and 21521005)the Program for Changjiang Scholars,Innovative Research Teams in Universities(no.IRT1205)the Fundamental Research Funds for the Central Universities(no.12060093063 and XK1803-05)。
文摘Transition metal phosphides are considered ideal alternatives for noble metal catalysts in hydrogen evolution reactions.In this study,amorphous NiCuFeP nanosheets were uniformly coated on self-supporting Cu_(3)P nanowire arrays through a facile electrodeposition method.The obtained_(3)D hierarchical NiCuFeP@Cu_(3)P/CF with good conductivity and abundant active sites was used as a hydrogen evolution reaction electrocatalyst.There are strong electronic interactions between each component of the material,as well as between the metal elements and P,which are conducive to improving the catalytic performance.
基金supported by the National Natural Science Foundation of China(No.22278380)China Postdoctoral Science Foundation(Nos.2024M762994 and GZC20232392)supported by the project of Yunnan Key Laboratory of Electromagnetic Materials and Devices,Yunnan University(No.ZZ2024009).
文摘Electrocatalytic conversion presents a promising alternative to conventional industrial catalysis.While aqueous-phase electrocatalysis has achieved notable advancements,oil-water immiscible systems remain challenging due to restricted reaction flux at multiphase interfaces.To address the limitation,we engineered a biphasic reaction system featuring a tailored oil-water catalytic interface in cyclohexene oxidation reaction(COR).The system employed a catalyst-loaded porous electrode as an active phase domain,enabling spatial separation of cyclohexene(organic phase)and electrolyte(aqueous phase).The tailored oil-water interface enhanced the interfacial mass transfer of substrate-catalysts and facilitated the spontaneous migration of 2-cyclohexen-1-ol into the aqueous phase,thereby streamlining product separation.Notably,polyaniline(PANI)modification on Co_(3)O_(4)enhanced surface lipophilicity,promoting cyclohexene adsorption and accelerating the COR catalytic kinetics(Co^(3+)-O+cyclohexene-H+e-→Co^(2+)-OH+2-cyclohexen-1-ol).The synergistic effects of optimized interfacial engineering and catalyst functionalization achieved exceptional performance:a current density of 45 mA·cm^(-2)at 1.6 V vs.reversible hydrogen electrode(V_(RHE)),coupled with 96.2%selectivity and 82.9%Faradaic efficiency.This work establishes an innovative paradigm for electrocatalytic conversions in oil-water immiscible systems through rational interface design and catalyst surface modulation.
基金supported by the National Natural Science Foundation of China(no.22278020 and 2177060378)the Program for Changjiang Scholars,Innovative Research Teams in Universities(no.IRT1205)the Fundamental Research Funds for the Central Universities(no.12060093063 and XK1803-05).
文摘Regulating the crystal plane exposure of catalysts is an effective way of enhancing their oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)activities.Herein,we have synthesized ultrathin metal phosphide(NiFeCuP)nanosheets via the topotactic transformation of layered double hydroxide(LDH)precursors,based on their tunable composition and special layered structure.These as-prepared metal phosphides not only inherit the ultrathin nanosheet structure of LDHs,but also maintain metal atomic dispersion of the LDH precursors,thus exposing more active sites and increasing their internal activity.Moreover,the presence of the heteroatomic Cu atom in ultrathin NiFeCuP nanosheets regulates the exposed crystal plane,that is,it induces the(210)crystal plane exposure and tunes the electronic structure to enhance OER and HER performances.Experiments combined with calculations indicate that ultrathin NiFeCuP nanosheets with surface reconstruction and regulated electronic structures optimize the ΔG value of the intermediates during the water splitting process,thereby exhibiting obviously improved HER and OER performances,and excellent overall water splitting activity.The prepared bi-functional catalyst exhibits an HER overpotential of 86 mV and an OER overpotential of 156 mV at 10 mA cm−2.This results in a low cell voltage of only 1.49 V to drive the overall water splitting in alkaline solutions.This work provides a new idea for the development of bi-functional catalysts exhibiting excellent performances by regulating the exposed crystal plane.
