Cobalt oxides have been widely investigated as promising replacements for noble metal-based catalysts for oxygen evolution reaction(OER). Herein, we, for the first time, have obtained porous CoxOy nanosheets with N-do...Cobalt oxides have been widely investigated as promising replacements for noble metal-based catalysts for oxygen evolution reaction(OER). Herein, we, for the first time, have obtained porous CoxOy nanosheets with N-doping and oxygen vacancies by etching Co3O4 nanosheets with NH3 plasma. Comparing with the pristine Co3O4 nanosheets(1.79 V), the porous CoxOy nanosheets with N-doping and oxygen vacancies have a much lower potential of 1.51 V versus RHE to reach the current density of 10 mA cm-2. The obtained sample has a lower Tafel slope of 68 m V dec-1 than the pristine Co3O4 nanosheets(234 mV dec-1).The disclosed Co^2+, which is responsible for the formation of active sites(CoOOH), N-doping and oxygen vacancies, gives rise to better performance of OER.展开更多
the types and strategies used to prepare defect electrocatalysts will continue to be studied and developed as new defective materials are generated.4. Characterization of defectsThis review briefly summarizes recent p...the types and strategies used to prepare defect electrocatalysts will continue to be studied and developed as new defective materials are generated.4. Characterization of defectsThis review briefly summarizes recent progress in defect electrocatalysts, and the synthesis strategies and characterization techniques for defects are systematically discussed. Although challenges in the characterization of defect structures in the electrocatalytic reaction process remain, the dynamic evolution of defect sites is predicted to be helpful for designing and preparing high-performance electrocatalysts for commercial applications. Furthermore, due to an insufficient understanding of the defect-structureproperty relationships, future possibilities for the reasonable design of defect electrocatalysts to obtain desirable performance are suggested.展开更多
Electro-oxidation of 5-hydroxymethylfurfural(HMFOR)is a promising green approach to realize the conversion of biomass into value-added chemicals.However,considering the complexity of the molecular structure of HMF,an ...Electro-oxidation of 5-hydroxymethylfurfural(HMFOR)is a promising green approach to realize the conversion of biomass into value-added chemicals.However,considering the complexity of the molecular structure of HMF,an in-depth understanding of the electrocatalytic behavior of HMFOR has rarely been investigated.Herein,the electrocatalytic mechanism of HMFOR on nickel nitride(Ni3 N)is elucidated by operando X-ray absorption spectroscopy(XAS),in situ Raman,quasi in situ X-ray photoelectron spectroscopy(XPS),and operando electrochemical impedance spectroscopy(EIS),respectively.The activity origin is proved to be Ni^(2+δ)N(OH)ads generated by the adsorbed hydroxyl group.Moreover,HMFOR on Ni3 N relates to a two-step reaction:Initially,the applied potential drives Ni atoms to lose electrons and adsorb OH-after 1.35 VRHE,giving rise to Ni^(2+δ)N(OH)ads with the electrophilic oxygen;then Ni^(2+δ)N(OH)ads seizes protons and electrons from HMF and leaves as H_(2) O spontaneously.Furthermore,the high electrolyte alkalinity favors the HMFOR process due to the increased active species(Ni^(2+δ)N(OH)ads)and the enhanced adsorption of HMF on the Ni3 N surface.This work could provide an in-depth understanding of the electrocatalytic mechanism of HMFOR on Ni3 N and demonstrate the alkalinity effect of the electrolyte on the electrocatalytic performance of HMFOR.展开更多
1.Introduction Hydrogen is an ideal energy carrier to tackle the energy crisis and greenhouse effect,because of its high energy density and low emission.The production,storage and transportation of hydrogen are key fa...1.Introduction Hydrogen is an ideal energy carrier to tackle the energy crisis and greenhouse effect,because of its high energy density and low emission.The production,storage and transportation of hydrogen are key factors to the practical application of hydrogen energy.As the scientific and technological understanding of the electrochemical devices was advancing in the past few decades,water electrolyzers based on the proton exchange membrane (PEM) have attracted much focus for its huge potential on the production of hydrogen via water splitting.PEM electrolyzers use perfluorinated sulfonic acid (PFSA) based membranes as the electrolyte.展开更多
High entropy oxides(HEOs) have attracted extensive attention of researchers due to their remarkable properties. The electrocatalytic activity of electrocatalysts is closely related to the reactivity of their surface a...High entropy oxides(HEOs) have attracted extensive attention of researchers due to their remarkable properties. The electrocatalytic activity of electrocatalysts is closely related to the reactivity of their surface atoms which usually shows a positive correlation. Excellenet stability of HEOs leads to their surface atoms with relative poor reactivity, limiting the applications for electrocatalysis. Therefore, it is significant to activate surface atoms of HEOs. Constructing amorphous structure, introducing oxygen defects and leaching are very effective strategies to improve the reactivity of surface atoms. Herein, to remove chemical inert, low-crystallinity(Fe, Co, Ni, Mn, Zn)_(3)O_(4) (HEO-Origin) nanosheets with abundant oxygen vacancies was synthesized, showing an excellent catalytic activity with an overpotential of 265 mV at 10 mA/cm^(2), which outperforms as-synthesized HEO-500℃-air(335 mV). The excellent catalytic performance of HEO-Origin can be attributed to high activity surface atoms, the introduction of oxygen defects efficiently altered electron distribution on the surface of HEO-Origin. Apart from, HEO-Origin also exhibits an outstanding electrochemical stability for oxygen evolution reaction(OER).展开更多
Stratigraphic hiatuses of variable time intervals within the Rhuddanian to early Aeronian(Llandovery, Silurian) are identified in the area bordering East Chongqing, West Hubei and Northwest Hunan in central China. The...Stratigraphic hiatuses of variable time intervals within the Rhuddanian to early Aeronian(Llandovery, Silurian) are identified in the area bordering East Chongqing, West Hubei and Northwest Hunan in central China. Their distribution suggested the existence of a local uplift, traditionally named the Yichang Uplift. The diachronous nature of the basal black shale of the Lungmachi Formation crossing different belts of this Uplift signifies the various developing stages during the uplifting process.The present paper defines the temporal and spatial distribution pattern of the Yichang Uplift, which might be one of the important controlling factors for the preservation and distribution of the shale gas in this region, as it has been demonstrated that the shale gas exploration is generally less promising in the areas where more of the basal part of the Lungmachi Formation is missing.Therefore, better understanding of the circumjacent distribution pattern developed throughout the uplifting process may provide the important guidance for the shale gas exploration. The present work is a sister study to the published paper, "Stage-progressive distribution pattern of the Lungmachian black graplolitic shales from Guizhou to Chongqing, Central China". These two studies thus provide a complete Ordovician-Silurian black shale distribution pattern in the Middle and Upper Yangtze, a region with the major shale gas fields in China.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.:51402100,21573066)
文摘Cobalt oxides have been widely investigated as promising replacements for noble metal-based catalysts for oxygen evolution reaction(OER). Herein, we, for the first time, have obtained porous CoxOy nanosheets with N-doping and oxygen vacancies by etching Co3O4 nanosheets with NH3 plasma. Comparing with the pristine Co3O4 nanosheets(1.79 V), the porous CoxOy nanosheets with N-doping and oxygen vacancies have a much lower potential of 1.51 V versus RHE to reach the current density of 10 mA cm-2. The obtained sample has a lower Tafel slope of 68 m V dec-1 than the pristine Co3O4 nanosheets(234 mV dec-1).The disclosed Co^2+, which is responsible for the formation of active sites(CoOOH), N-doping and oxygen vacancies, gives rise to better performance of OER.
基金supported by grants from the National Natural Science Foundation of China (Grant Nos. 21573066, 21825201, 2187350, 51402100 and 21905088)。
文摘the types and strategies used to prepare defect electrocatalysts will continue to be studied and developed as new defective materials are generated.4. Characterization of defectsThis review briefly summarizes recent progress in defect electrocatalysts, and the synthesis strategies and characterization techniques for defects are systematically discussed. Although challenges in the characterization of defect structures in the electrocatalytic reaction process remain, the dynamic evolution of defect sites is predicted to be helpful for designing and preparing high-performance electrocatalysts for commercial applications. Furthermore, due to an insufficient understanding of the defect-structureproperty relationships, future possibilities for the reasonable design of defect electrocatalysts to obtain desirable performance are suggested.
基金supported by the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(Grant No.:21902047)+1 种基金the Provincial Natural Science Foundation of Hunan(2020JJ5045)the Fundamental Research Funds for the Central Universities(Grant No.531118010127)。
文摘Electro-oxidation of 5-hydroxymethylfurfural(HMFOR)is a promising green approach to realize the conversion of biomass into value-added chemicals.However,considering the complexity of the molecular structure of HMF,an in-depth understanding of the electrocatalytic behavior of HMFOR has rarely been investigated.Herein,the electrocatalytic mechanism of HMFOR on nickel nitride(Ni3 N)is elucidated by operando X-ray absorption spectroscopy(XAS),in situ Raman,quasi in situ X-ray photoelectron spectroscopy(XPS),and operando electrochemical impedance spectroscopy(EIS),respectively.The activity origin is proved to be Ni^(2+δ)N(OH)ads generated by the adsorbed hydroxyl group.Moreover,HMFOR on Ni3 N relates to a two-step reaction:Initially,the applied potential drives Ni atoms to lose electrons and adsorb OH-after 1.35 VRHE,giving rise to Ni^(2+δ)N(OH)ads with the electrophilic oxygen;then Ni^(2+δ)N(OH)ads seizes protons and electrons from HMF and leaves as H_(2) O spontaneously.Furthermore,the high electrolyte alkalinity favors the HMFOR process due to the increased active species(Ni^(2+δ)N(OH)ads)and the enhanced adsorption of HMF on the Ni3 N surface.This work could provide an in-depth understanding of the electrocatalytic mechanism of HMFOR on Ni3 N and demonstrate the alkalinity effect of the electrolyte on the electrocatalytic performance of HMFOR.
基金supported by the National Key R&D Program of China(2021YFA1500900,2020YFA0710000)the National Natural Science Foundation of China(22172047,22002039,21825201 and U19A2017)+3 种基金the Provincial Natural Science Foundation of Hunan(2021JJ30089,2016TP1009 and 2020JJ5045)the China Postdoctoral Science Foundation(2019M662759,2020M682541 and 2020M682549)the Shenzhen Science and Technology Program(JCYJ20210324122209025)the Changsha Municipal Natural Science Foundation(kq2107008 and kq2007009)。
文摘1.Introduction Hydrogen is an ideal energy carrier to tackle the energy crisis and greenhouse effect,because of its high energy density and low emission.The production,storage and transportation of hydrogen are key factors to the practical application of hydrogen energy.As the scientific and technological understanding of the electrochemical devices was advancing in the past few decades,water electrolyzers based on the proton exchange membrane (PEM) have attracted much focus for its huge potential on the production of hydrogen via water splitting.PEM electrolyzers use perfluorinated sulfonic acid (PFSA) based membranes as the electrolyte.
基金supported by the National Natural Science Foundation of China(Nos.U19A2017,21902047,51402100,21825201,21573066,and 21905088)the Provincial Natural Science Foundation of Hunan(Nos.2020JJ5044,2022JJ10006)。
文摘High entropy oxides(HEOs) have attracted extensive attention of researchers due to their remarkable properties. The electrocatalytic activity of electrocatalysts is closely related to the reactivity of their surface atoms which usually shows a positive correlation. Excellenet stability of HEOs leads to their surface atoms with relative poor reactivity, limiting the applications for electrocatalysis. Therefore, it is significant to activate surface atoms of HEOs. Constructing amorphous structure, introducing oxygen defects and leaching are very effective strategies to improve the reactivity of surface atoms. Herein, to remove chemical inert, low-crystallinity(Fe, Co, Ni, Mn, Zn)_(3)O_(4) (HEO-Origin) nanosheets with abundant oxygen vacancies was synthesized, showing an excellent catalytic activity with an overpotential of 265 mV at 10 mA/cm^(2), which outperforms as-synthesized HEO-500℃-air(335 mV). The excellent catalytic performance of HEO-Origin can be attributed to high activity surface atoms, the introduction of oxygen defects efficiently altered electron distribution on the surface of HEO-Origin. Apart from, HEO-Origin also exhibits an outstanding electrochemical stability for oxygen evolution reaction(OER).
基金supported by the Strategic Priority Research Program of Chinese Academy of Sciences (Grant No. XDB26000000)the National Natural Science Foundation of China (Grant Nos. U1562213 and 41502025)the National Science and Technology Major Project of China (Grant No. 2017ZX05035002-001)
文摘Stratigraphic hiatuses of variable time intervals within the Rhuddanian to early Aeronian(Llandovery, Silurian) are identified in the area bordering East Chongqing, West Hubei and Northwest Hunan in central China. Their distribution suggested the existence of a local uplift, traditionally named the Yichang Uplift. The diachronous nature of the basal black shale of the Lungmachi Formation crossing different belts of this Uplift signifies the various developing stages during the uplifting process.The present paper defines the temporal and spatial distribution pattern of the Yichang Uplift, which might be one of the important controlling factors for the preservation and distribution of the shale gas in this region, as it has been demonstrated that the shale gas exploration is generally less promising in the areas where more of the basal part of the Lungmachi Formation is missing.Therefore, better understanding of the circumjacent distribution pattern developed throughout the uplifting process may provide the important guidance for the shale gas exploration. The present work is a sister study to the published paper, "Stage-progressive distribution pattern of the Lungmachian black graplolitic shales from Guizhou to Chongqing, Central China". These two studies thus provide a complete Ordovician-Silurian black shale distribution pattern in the Middle and Upper Yangtze, a region with the major shale gas fields in China.