Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the in...Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the intrinsic activity of Ni and Co catalytic centers.However,the dynamic evolution and atomic-scale synergy between these centers remain elusive.Herein,we fabricated NiCo_(2)O_(4)nanosheets supported on nickel foam,where Ni preferentially occupies tetrahedral sites to regulate the electronic configuration of octahedral Co.Experimental and theoretical results demonstrate that the incorporation of tetrahedral Ni induces low-to-intermediate spin transition in octahedral Co,thereby optimizing eg orbital occupancy and stabilizing active sites.This spin-state engineering establishes Ni-Co synergistic catalytic centers for the selective oxidation of glucose to formate(FA).At higher potential(≥1.4 V vs.RHE),octahedral Co undergoes reconstruction into excessive active CoOOH and CoO_(2)species,resulting in glucose overoxidation to CO_(2)and intensified competitive oxygen evolution.In contrast,at lower potentials(<1.4 V vs.RHE),tetrahedral Ni facilitates electron delocalization across the Ni–O–Co lattice,thereby stabilizing octahedral Co for glucose adsorption and oxidation.Subsequently,a coupled electrocatalytic system was constructed,achieving 80.7%FA yield with 91.3%Faradaic efficiency(FE)at NiCo_(2)O_(4)anode and H2 evolution rate of 696μmol h^(−1)with 99.9%FE at Pt cathode for 2 h under 1.35 V vs.RHE.This work provides a deep insight into spin-state regulation of the catalytic center,offering valuable guidance for rational catalyst design.展开更多
Efficient electrocatalysts are vital to large-current hydrogen production in commercial water splitting for green energy generation.Herein,a novel heterophase engineering strategy is described to produce polymorphic C...Efficient electrocatalysts are vital to large-current hydrogen production in commercial water splitting for green energy generation.Herein,a novel heterophase engineering strategy is described to produce polymorphic CoSe_(2)electrocatalysts.The composition of the electrocatalysts consisting of both cubic CoSe_(2)(c-CoSe_(2))and orthorhombic CoSe_(2)(o-CoSe_(2))phases can be controlled precisely.Our results demonstrate that junction-induced spin-state modulation of Co atoms enhances the adsorption of intermediates and accelerates charge transfer resulting in superior large-current hydrogen evolution reaction(HER)properties.Specifically,the CoSe_(2)based heterophase catalyst with the optimal c-CoSe_(2)content requires an overpotential of merely 240 mV to achieve 1,000 mA·cm^(-2)as well as a Tafel slope of 50.4 mV·dec^(-1).Furthermore,the electrocatalyst can maintain a large current density of 1,500 mA·cm^(-2)for over 320 h without decay.The results reveal the advantages and potential of heterophase junction engineering pertaining to design and fabrication of low-cost transition metal catalysts for large-current water splitting.展开更多
Matter-wave interferometers with spin quantum states are attractive in quantum manipulation and precision measurements. Here, five spatial interference patterns corresponding to the full spin states are observed in ea...Matter-wave interferometers with spin quantum states are attractive in quantum manipulation and precision measurements. Here, five spatial interference patterns corresponding to the full spin states are observed in each run of the experiment, by the combination of the Majorana transition according to the exponential modulation of the magnetic field pulse decline curve and radio frequency coupling among multiple magnetic sub-states.Compared to the realization of two Majorana transitions, the interference fringe for the magnetic field insensitive state also has a higher contrast. After spatially overlapping the full magnetic sub-state interference patterns dozens of times in consecutive experimental measurements, clear fringes are still observed, indicating the great stability of the relative phases of different components. This indicates the potential to achieve an interferometer with multiple spin clocks.展开更多
Room-temperature switchable materials showing multiple responses toward external stimuli are highly desired.Herein,we report bidirectional spin-state switch and fluorescence modulation of an Fe(II)complex(1)based on a...Room-temperature switchable materials showing multiple responses toward external stimuli are highly desired.Herein,we report bidirectional spin-state switch and fluorescence modulation of an Fe(II)complex(1)based on a rhodamine B 2-pyridinecarbaldehyde hydrazone ligand in both the solid state and solution.The complex is predominantly stabilized in the low-spin(LS)state at room temperature due to the strong ligand-field strength imposed by acylhydrazone pyridine.展开更多
基金financially supported by the National Natural Science Foundation of China (22472199)Chinese Universities Scientific Fund (15055009)Central University Guided Funds for Building World-Class Universities (Disciplines) and Advancing Characteristic Development
文摘Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the intrinsic activity of Ni and Co catalytic centers.However,the dynamic evolution and atomic-scale synergy between these centers remain elusive.Herein,we fabricated NiCo_(2)O_(4)nanosheets supported on nickel foam,where Ni preferentially occupies tetrahedral sites to regulate the electronic configuration of octahedral Co.Experimental and theoretical results demonstrate that the incorporation of tetrahedral Ni induces low-to-intermediate spin transition in octahedral Co,thereby optimizing eg orbital occupancy and stabilizing active sites.This spin-state engineering establishes Ni-Co synergistic catalytic centers for the selective oxidation of glucose to formate(FA).At higher potential(≥1.4 V vs.RHE),octahedral Co undergoes reconstruction into excessive active CoOOH and CoO_(2)species,resulting in glucose overoxidation to CO_(2)and intensified competitive oxygen evolution.In contrast,at lower potentials(<1.4 V vs.RHE),tetrahedral Ni facilitates electron delocalization across the Ni–O–Co lattice,thereby stabilizing octahedral Co for glucose adsorption and oxidation.Subsequently,a coupled electrocatalytic system was constructed,achieving 80.7%FA yield with 91.3%Faradaic efficiency(FE)at NiCo_(2)O_(4)anode and H2 evolution rate of 696μmol h^(−1)with 99.9%FE at Pt cathode for 2 h under 1.35 V vs.RHE.This work provides a deep insight into spin-state regulation of the catalytic center,offering valuable guidance for rational catalyst design.
基金financially supported by the National Natural Science Foundation of China(Nos.52002294 and 52202111)the Key Research and Development Program of Hubei Province(No.2021BAA208)+3 种基金the Knowledge Innovation Program of Wuhan-Shuguang Project(No.2022010801020364)City University of Hong Kong Donation Research Grant(No.DON-RMG 9229021)City University of Hong Kong Donation Grant(No.9220061)City University of Hong Kong Strategic Research Grant(SRG)(No.7005505)。
文摘Efficient electrocatalysts are vital to large-current hydrogen production in commercial water splitting for green energy generation.Herein,a novel heterophase engineering strategy is described to produce polymorphic CoSe_(2)electrocatalysts.The composition of the electrocatalysts consisting of both cubic CoSe_(2)(c-CoSe_(2))and orthorhombic CoSe_(2)(o-CoSe_(2))phases can be controlled precisely.Our results demonstrate that junction-induced spin-state modulation of Co atoms enhances the adsorption of intermediates and accelerates charge transfer resulting in superior large-current hydrogen evolution reaction(HER)properties.Specifically,the CoSe_(2)based heterophase catalyst with the optimal c-CoSe_(2)content requires an overpotential of merely 240 mV to achieve 1,000 mA·cm^(-2)as well as a Tafel slope of 50.4 mV·dec^(-1).Furthermore,the electrocatalyst can maintain a large current density of 1,500 mA·cm^(-2)for over 320 h without decay.The results reveal the advantages and potential of heterophase junction engineering pertaining to design and fabrication of low-cost transition metal catalysts for large-current water splitting.
基金Supported by the National Key Research and Development Program of China under Grant No 2016YFA0301501the National Natural Science Foundation of China under Grant Nos 61727819 and 91736208
文摘Matter-wave interferometers with spin quantum states are attractive in quantum manipulation and precision measurements. Here, five spatial interference patterns corresponding to the full spin states are observed in each run of the experiment, by the combination of the Majorana transition according to the exponential modulation of the magnetic field pulse decline curve and radio frequency coupling among multiple magnetic sub-states.Compared to the realization of two Majorana transitions, the interference fringe for the magnetic field insensitive state also has a higher contrast. After spatially overlapping the full magnetic sub-state interference patterns dozens of times in consecutive experimental measurements, clear fringes are still observed, indicating the great stability of the relative phases of different components. This indicates the potential to achieve an interferometer with multiple spin clocks.
基金supported by the National Natural Science Foundation of China(nos.21871140 and 21401104).
文摘Room-temperature switchable materials showing multiple responses toward external stimuli are highly desired.Herein,we report bidirectional spin-state switch and fluorescence modulation of an Fe(II)complex(1)based on a rhodamine B 2-pyridinecarbaldehyde hydrazone ligand in both the solid state and solution.The complex is predominantly stabilized in the low-spin(LS)state at room temperature due to the strong ligand-field strength imposed by acylhydrazone pyridine.
