Hydrothermal carbonization(HTC) is a valuable approach to convert furfural residue(FR) into carbon material. The prepared biochars are usually characterized comprehensively, while the stock process water still remains...Hydrothermal carbonization(HTC) is a valuable approach to convert furfural residue(FR) into carbon material. The prepared biochars are usually characterized comprehensively, while the stock process water still remains to be studied in detail. Herein, a NMR study of the main components in stock process water generated at different HTC reaction conditions was reported. Various qualitative and quantitative NMR techniques(~1H and ^(13)C NMR,~1H-~1H COSY and ~1H-^(13)C HSQC etc.) especially 1D selective gradient total correlation spectroscopy(TOCSY NMR) were strategically applied in the analysis of HTC stock process water. Without separation and purification, it was demonstrated that the main detectable compounds are 5-hydroxymethylfurfural, formic acid, methanol, acetic acid, levulinic acid, glycerol, hydroxyacetone and acetaldehyde in this complicate mixture. Furthermore, the relationship between the concentration of major products and the reaction conditions(180-240 ℃ at 8 h, and 1-24 h at 240 ℃) was established. Finally, reasonable reaction pathways for hydrothermal conversion of FR were proposed based on this result and our previously obtained characteristics of biochars. The routine and challenging NMR methods utilized here would be an alternative other than HPLC or GC for biomass conversion research and can be extended to more studies.展开更多
Tunable carrier density plays a key role in the investigation of novel transport properties in three-dimensional topological semimetals.We demonstrate that the carrier density,as well as the mobility,of Dirac semimeta...Tunable carrier density plays a key role in the investigation of novel transport properties in three-dimensional topological semimetals.We demonstrate that the carrier density,as well as the mobility,of Dirac semimetal Cd_(3)As_(2) nanoplates can be effectively tuned via in situ thermal treatment at 350 K for one hour,resulting in non-monotonic evolution by virtue of the thermal cycling treatments.The upward shift of Fermi level relative to the Dirac nodes blurs the surface Fermi-arc states,accompanied by an anomalous phase shift in the oscillations of bulk states,due to a change in the topology of the electrons.Meanwhile,the oscillation peaks of bulk longitudinal magnetoresistivity shift at high fields,due to their coupling to the oscillations of the surface Fermi-arc states.Our work provides a thermal control mechanism for the manipulation of quantum states in Dirac semimetal Cd_(3)As_(2) at high temperatures,via their carrier density.展开更多
The hydrogen evolution reaction(HER)of molybdenum disulfide(MoS_(2))is limited in alkaline and acid solution because the active sites are on the finite edge with extended basal plane remaining inert.Herein,we activate...The hydrogen evolution reaction(HER)of molybdenum disulfide(MoS_(2))is limited in alkaline and acid solution because the active sites are on the finite edge with extended basal plane remaining inert.Herein,we activated the interfacial S sites by coupling with Ru nanoparticles on the inert basal plane of MoS_(2)nanosheets.The density functional theory(DFT)calculation and experimental results show that the interfacial S electronic structure was modulated.And the results of∆G H*demonstrate that the adsorption of H on the MoS_(2)was also optimized.With the advantage of interfacial S sites activation,the Ru-MoS_(2)needs only overpotential of 110 and 98 mV to achieve 10 mA·cm^(–2)in both 0.5 M H_(2)SO_(4)and ^(1) M KOH solution,respectively.This strategy paves a new way for activating the basal plane of other transition metal sulfide electrocatalysts for improving the HER performance.展开更多
The electrocatalytic hydrogen evolution reaction(HER)is one of the most promising ways for low-cost hydrogen production in the future.In this work,hetero S atoms were introduced into the MoO2 to enhance the catalytic ...The electrocatalytic hydrogen evolution reaction(HER)is one of the most promising ways for low-cost hydrogen production in the future.In this work,hetero S atoms were introduced into the MoO2 to enhance the catalytic activity by simultaneously adjusting electron structure,engineering lattice defect,and increasing oxygen vacancies.And the S doped MoO2 nanosheets with proper S doping amount show the enhanced performance for HER.The optimized catalyst shows a small onset overpotential as low as 120 mV,a low overpotential of 176 mV at the current density of 10 mA/cm^2 which is decreased 166 mV compared to that of the pristine MoO2 nanosheets,a low Tafel slope of 57 mV/decade,and a high turnover frequency of 0.13 H2/s per active site at 150 mV.This finding proposes an effective strategy to prepare nonprecious metal oxide catalyst for enhancing HER performance by rationally doping hetero atoms.展开更多
基金Supported by Shanxi Scholarship Council of China (2015-123)the Natural Science Foundation of China (51602322)the Key Research and Development Program of Shanxi Province (International Cooperation) (201703D421041) for financial support
文摘Hydrothermal carbonization(HTC) is a valuable approach to convert furfural residue(FR) into carbon material. The prepared biochars are usually characterized comprehensively, while the stock process water still remains to be studied in detail. Herein, a NMR study of the main components in stock process water generated at different HTC reaction conditions was reported. Various qualitative and quantitative NMR techniques(~1H and ^(13)C NMR,~1H-~1H COSY and ~1H-^(13)C HSQC etc.) especially 1D selective gradient total correlation spectroscopy(TOCSY NMR) were strategically applied in the analysis of HTC stock process water. Without separation and purification, it was demonstrated that the main detectable compounds are 5-hydroxymethylfurfural, formic acid, methanol, acetic acid, levulinic acid, glycerol, hydroxyacetone and acetaldehyde in this complicate mixture. Furthermore, the relationship between the concentration of major products and the reaction conditions(180-240 ℃ at 8 h, and 1-24 h at 240 ℃) was established. Finally, reasonable reaction pathways for hydrothermal conversion of FR were proposed based on this result and our previously obtained characteristics of biochars. The routine and challenging NMR methods utilized here would be an alternative other than HPLC or GC for biomass conversion research and can be extended to more studies.
基金the National Key Research and Development Program of China(Grant No.2016YFA0401003)the National Natural Science Foundation of China(Grant Nos.11804340,11774353,U19A2093,and U1732274)the CAS/SAFEA International Partnership Program for Creative Research Teams of China。
文摘Tunable carrier density plays a key role in the investigation of novel transport properties in three-dimensional topological semimetals.We demonstrate that the carrier density,as well as the mobility,of Dirac semimetal Cd_(3)As_(2) nanoplates can be effectively tuned via in situ thermal treatment at 350 K for one hour,resulting in non-monotonic evolution by virtue of the thermal cycling treatments.The upward shift of Fermi level relative to the Dirac nodes blurs the surface Fermi-arc states,accompanied by an anomalous phase shift in the oscillations of bulk states,due to a change in the topology of the electrons.Meanwhile,the oscillation peaks of bulk longitudinal magnetoresistivity shift at high fields,due to their coupling to the oscillations of the surface Fermi-arc states.Our work provides a thermal control mechanism for the manipulation of quantum states in Dirac semimetal Cd_(3)As_(2) at high temperatures,via their carrier density.
基金the National Natural Science Foundation of China(Nos.51871078 and 52071119)Heilongjiang Science Foundation(No.E201808).
文摘The hydrogen evolution reaction(HER)of molybdenum disulfide(MoS_(2))is limited in alkaline and acid solution because the active sites are on the finite edge with extended basal plane remaining inert.Herein,we activated the interfacial S sites by coupling with Ru nanoparticles on the inert basal plane of MoS_(2)nanosheets.The density functional theory(DFT)calculation and experimental results show that the interfacial S electronic structure was modulated.And the results of∆G H*demonstrate that the adsorption of H on the MoS_(2)was also optimized.With the advantage of interfacial S sites activation,the Ru-MoS_(2)needs only overpotential of 110 and 98 mV to achieve 10 mA·cm^(–2)in both 0.5 M H_(2)SO_(4)and ^(1) M KOH solution,respectively.This strategy paves a new way for activating the basal plane of other transition metal sulfide electrocatalysts for improving the HER performance.
基金supported by the Research Project of the Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education(2017005)the National Natural Science Foundation of China(Nos.51571072 and 51871078)Heilongjiang Science Foundation(No.E2018028).
文摘The electrocatalytic hydrogen evolution reaction(HER)is one of the most promising ways for low-cost hydrogen production in the future.In this work,hetero S atoms were introduced into the MoO2 to enhance the catalytic activity by simultaneously adjusting electron structure,engineering lattice defect,and increasing oxygen vacancies.And the S doped MoO2 nanosheets with proper S doping amount show the enhanced performance for HER.The optimized catalyst shows a small onset overpotential as low as 120 mV,a low overpotential of 176 mV at the current density of 10 mA/cm^2 which is decreased 166 mV compared to that of the pristine MoO2 nanosheets,a low Tafel slope of 57 mV/decade,and a high turnover frequency of 0.13 H2/s per active site at 150 mV.This finding proposes an effective strategy to prepare nonprecious metal oxide catalyst for enhancing HER performance by rationally doping hetero atoms.