The neutral hydrogen evolution reaction(HER)is vital in the chemical industry,and its efficiency depends on the interior character of the catalyst.Herein,work function(WF)engineering is introduced via 3d metal(Fe,Co,N...The neutral hydrogen evolution reaction(HER)is vital in the chemical industry,and its efficiency depends on the interior character of the catalyst.Herein,work function(WF)engineering is introduced via 3d metal(Fe,Co,Ni,and Cu)doping for modulating the Fermi energy level of Mo2C.The defective energy level facilitates the free water molecule adsorption and,subsequently,promotes the neutral HER efficiency.Specifically,at a current density of 10 mA/cm2,Cu-Mo2C exhibits the best HER performance with an overpotential of 78 mV,followed by Ni-Mo2C,Co-Mo2C,Fe-Mo2C,and bare Mo2C with 90,95,100,and 173 mV,respectively,and the corresponding Tafel slope values are 40,43,42,56,and 102 mV/dec.The modified WF can also lead to an enhanced photocatalytic efficiency owing to the lowered Schottky barrier and excellent carrier transition across the electrocatalyst–solution interface.When coupling the metal-doped Mo2C samples with TiO2,enhanced photocatalytic neutral HER rates are obtained in comparison to the case with bare TiO2.Typically,the HER rates are 521,404,275,224,147,and 112μmol/h for Cu,Ni,Co,Fe,bare Mo2C,and bare TiO2,respectively.Time-resolved photoluminescence spectroscopy(TRPS)and ultrafast transient absorption(TA)measurements are carried out to confirm the recombination and migration of the photogenerated carriers.The fittedτvalues from the TRPS curves are 22.6,20.5,10.1,4.7,4.0,2.5,and 1.9 ns for TiO2,TiO2-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,and TiO2-Pt,respectively.Additionally,the fittedτvalues from the TA results are 31,73,and 105 ps for the TiO2-Mo2C,TiO2-Cu-Mo2C,and TiO2-Pt samples,respectively.This work provides in-depth insights into the WF modulation of an electrocatalyst for improving the HER performance.展开更多
One of the most primary challenges to achieve large-scale hydrogen generation from water electrolysis is the sluggish kinetics and noble metal dependence of cathodic hydrogen evolution reaction(HER).By considering the...One of the most primary challenges to achieve large-scale hydrogen generation from water electrolysis is the sluggish kinetics and noble metal dependence of cathodic hydrogen evolution reaction(HER).By considering the excellent water dissociation catalytic activity of Mo2C, abundant Pt/Mo2C interfaces were facilely engineered via galvanic replacement(gr) by using Mo/Mo2C nanosheets as self-sacrificed templates to alter the alkaline HER mechanism on Pt based catalyst. The rational designed interface-rich gr-Pt/Mo2C catalyst exhibited excellent activity with the overpotential to drive 10 mA/cm2 current density decreased by 18.5 mV compared with the commercial Pt/C catalyst. 34.3 mV/dec Tafel slope confirms the Volmer-Tafel HER route on gr-Pt/Mo2C in alkaline condition. Platinum utilization is calculated to be improved by 9.7 times by considered the low Pt loading in the gr-Pt/Mo2C catalyst. With its satisfied stability, the scalable gr-Pt/Mo2C catalyst shows promising application potential in industrial electrolysis systems.展开更多
Graphene-based heterostructure is one of the most attractive topics in physics and material sciences due to its intriguing properties and applications. We report the one-step fabrication of a novel graphene/Mo2C heter...Graphene-based heterostructure is one of the most attractive topics in physics and material sciences due to its intriguing properties and applications. We report the one-step fabrication of a novel graphene/Mo2C heterostructure by using chemical vapor deposition（CVD）. The composition and structure of the heterostructure are characterized through energydispersive spectrometer, transmission electron microscope, and Raman spectrum. The growth rule analysis of the results shows the flow rate of methane is a main factor in preparing the graphene/Mo2C heterostructure. A schematic diagram of the growth process is also established. Transport measurements are performed to study the superconductivity of the heterostructure which has potential applications in superconducting devices.展开更多
Hierarchical mesoporous MoO2/Mo2C/C microspheres,which are composed of primary nanoparticles with a size of about 30 nm,have been designed and synthesized through polymer regulation and subsequent carbonization proces...Hierarchical mesoporous MoO2/Mo2C/C microspheres,which are composed of primary nanoparticles with a size of about 30 nm,have been designed and synthesized through polymer regulation and subsequent carbonization processes.The as-synthesized microspheres were characterized by XRD,Raman,SEM,TEM,XPS measurements and so on.It was found that polyethylene glycol acted as a structure-directing agent,mild reducing agent and carbon source in the formation of these hierarchical mesoporous Mo O2/Mo2C/C microspheres.Moreover,the electrochemical property of the microspheres was also investigated in this work.Evaluated as an anode material for lithium ion batteries,the hierarchical mesoporous Mo O2/Mo2C/C electrode delivered the discharge specific capacities of 665 and 588 m Ah/g after 100 cycles at current densities of 100 and 200 m A/g,respectively.The satisfactory cycling performance and controllable process facilitate the practical applications of the hierarchical mesoporous Mo O2/Mo2C/C as a potential anode material in high-energy density lithium-ion batteries.展开更多
Focused exploration of earth-abundant and cost-efficient non-noble metal electrocatalysts with superior hydrogen evolution reaction(HER)performance is very important for large-scale and efficient electrolysis of water...Focused exploration of earth-abundant and cost-efficient non-noble metal electrocatalysts with superior hydrogen evolution reaction(HER)performance is very important for large-scale and efficient electrolysis of water.Herein,a sandwich composite structure(designed as MS-Mo2C@NCNS)ofβ-Mo2C hollow nanotubes(HNT)and N-doped carbon nanosheets(NCNS)is designed and prepared using a binary NaCl–KCl molten salt(MS)strategy for HER.The temperature-dominant Kirkendall formation mechanism is tentatively proposed for such a three-dimensional hierarchical framework.Due to its attractive structure and componential synergism,MS-Mo2C@NCNS exposes more effective active sites,confers robust structural stability,and shows significant electrocatalytic activity/stability in HER,with a current density of 10 mA cm-2 and an overpotential of only 98 mV in 1 M KOH.Density functional theory calculations point to the synergistic effect of Mo2C HNT and NCNS,leading to enhanced electronic transport and suitable adsorption free energies of H*(ΔGH*)on the surface of electroactive Mo2C.More significantly,the MS-assisted synthetic methodology here provides an enormous perspective for the commercial development of highly active non-noble metal electrocatalysts toward efficient hydrogen evolution.展开更多
Precise spatial control of 2D materials is the key capability of engineering their optical,electronic,and mechanical properties.However,growth of novel 2D Mo2C on Cu surface by chemical vapor deposition method was rev...Precise spatial control of 2D materials is the key capability of engineering their optical,electronic,and mechanical properties.However,growth of novel 2D Mo2C on Cu surface by chemical vapor deposition method was revealed to be seed-induced 2D growth,limiting further synthesis of complex Mo2C spatial structures.In this research,we demonstrate the controlled growth of Mo2C pyramids with numerous morphologies,which are characterized with clear terraces within the structures.The whole evolution for Mo2C pyramids in the coursed of CVD process has been detected,posing significant potential in probing growth mechanism.The formation of the Mo2C pyramids arises from the supersaturation-induced nucleation and concentration-gradient driven diffused growth of a new Mo2C layer on the edged areas of intrinsic ones,as supported by STEM imaging.This work provides a novel Mo2C-based pyramid structure and further reveals a sliding growth mechanism,which could offer impetus for the design of new 3D spatial structures of Mo2C and other 2D materials.展开更多
文摘The neutral hydrogen evolution reaction(HER)is vital in the chemical industry,and its efficiency depends on the interior character of the catalyst.Herein,work function(WF)engineering is introduced via 3d metal(Fe,Co,Ni,and Cu)doping for modulating the Fermi energy level of Mo2C.The defective energy level facilitates the free water molecule adsorption and,subsequently,promotes the neutral HER efficiency.Specifically,at a current density of 10 mA/cm2,Cu-Mo2C exhibits the best HER performance with an overpotential of 78 mV,followed by Ni-Mo2C,Co-Mo2C,Fe-Mo2C,and bare Mo2C with 90,95,100,and 173 mV,respectively,and the corresponding Tafel slope values are 40,43,42,56,and 102 mV/dec.The modified WF can also lead to an enhanced photocatalytic efficiency owing to the lowered Schottky barrier and excellent carrier transition across the electrocatalyst–solution interface.When coupling the metal-doped Mo2C samples with TiO2,enhanced photocatalytic neutral HER rates are obtained in comparison to the case with bare TiO2.Typically,the HER rates are 521,404,275,224,147,and 112μmol/h for Cu,Ni,Co,Fe,bare Mo2C,and bare TiO2,respectively.Time-resolved photoluminescence spectroscopy(TRPS)and ultrafast transient absorption(TA)measurements are carried out to confirm the recombination and migration of the photogenerated carriers.The fittedτvalues from the TRPS curves are 22.6,20.5,10.1,4.7,4.0,2.5,and 1.9 ns for TiO2,TiO2-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,and TiO2-Pt,respectively.Additionally,the fittedτvalues from the TA results are 31,73,and 105 ps for the TiO2-Mo2C,TiO2-Cu-Mo2C,and TiO2-Pt samples,respectively.This work provides in-depth insights into the WF modulation of an electrocatalyst for improving the HER performance.
基金financial support from the National Natural Science Foundation of China (Nos.21875224 and 21703211)the Natural Science Foundation of Zhejiang Province (No.LGG19B030001)。
文摘One of the most primary challenges to achieve large-scale hydrogen generation from water electrolysis is the sluggish kinetics and noble metal dependence of cathodic hydrogen evolution reaction(HER).By considering the excellent water dissociation catalytic activity of Mo2C, abundant Pt/Mo2C interfaces were facilely engineered via galvanic replacement(gr) by using Mo/Mo2C nanosheets as self-sacrificed templates to alter the alkaline HER mechanism on Pt based catalyst. The rational designed interface-rich gr-Pt/Mo2C catalyst exhibited excellent activity with the overpotential to drive 10 mA/cm2 current density decreased by 18.5 mV compared with the commercial Pt/C catalyst. 34.3 mV/dec Tafel slope confirms the Volmer-Tafel HER route on gr-Pt/Mo2C in alkaline condition. Platinum utilization is calculated to be improved by 9.7 times by considered the low Pt loading in the gr-Pt/Mo2C catalyst. With its satisfied stability, the scalable gr-Pt/Mo2C catalyst shows promising application potential in industrial electrolysis systems.
基金supported by the National Natural Science Foundation of China(Grant Nos.1402342,11574338,and 11274333)the Hundred Talents Program of Chinese Academy of Sciences,the International Collaboration and Innovation Program on High Mobility Materials Engineering,Chinese Academy of Sciences(Grant No.KGZD-EW-303)the“Strategic Priority Research Program(B)”of the Chinese Academy of Sciences(Grant No.XDB04040300)
文摘Graphene-based heterostructure is one of the most attractive topics in physics and material sciences due to its intriguing properties and applications. We report the one-step fabrication of a novel graphene/Mo2C heterostructure by using chemical vapor deposition（CVD）. The composition and structure of the heterostructure are characterized through energydispersive spectrometer, transmission electron microscope, and Raman spectrum. The growth rule analysis of the results shows the flow rate of methane is a main factor in preparing the graphene/Mo2C heterostructure. A schematic diagram of the growth process is also established. Transport measurements are performed to study the superconductivity of the heterostructure which has potential applications in superconducting devices.
基金supported by the National Natural Science Foundation of China(No.21376251 and 21406233)the National Basic Research Development Program of China(2013CB632600)
文摘Hierarchical mesoporous MoO2/Mo2C/C microspheres,which are composed of primary nanoparticles with a size of about 30 nm,have been designed and synthesized through polymer regulation and subsequent carbonization processes.The as-synthesized microspheres were characterized by XRD,Raman,SEM,TEM,XPS measurements and so on.It was found that polyethylene glycol acted as a structure-directing agent,mild reducing agent and carbon source in the formation of these hierarchical mesoporous Mo O2/Mo2C/C microspheres.Moreover,the electrochemical property of the microspheres was also investigated in this work.Evaluated as an anode material for lithium ion batteries,the hierarchical mesoporous Mo O2/Mo2C/C electrode delivered the discharge specific capacities of 665 and 588 m Ah/g after 100 cycles at current densities of 100 and 200 m A/g,respectively.The satisfactory cycling performance and controllable process facilitate the practical applications of the hierarchical mesoporous Mo O2/Mo2C/C as a potential anode material in high-energy density lithium-ion batteries.
基金the National Natural Science Foundation of China(Nos.52072151,52171211,52102253,52271218,U22A20145)the Jinan Independent Innovative Team(2020GXRC015)+1 种基金the Major Program of Shandong Province Natural Science Foundation(ZR2021ZD05)the Science and Technology Program of University of Jinan(XKY2119).
文摘Focused exploration of earth-abundant and cost-efficient non-noble metal electrocatalysts with superior hydrogen evolution reaction(HER)performance is very important for large-scale and efficient electrolysis of water.Herein,a sandwich composite structure(designed as MS-Mo2C@NCNS)ofβ-Mo2C hollow nanotubes(HNT)and N-doped carbon nanosheets(NCNS)is designed and prepared using a binary NaCl–KCl molten salt(MS)strategy for HER.The temperature-dominant Kirkendall formation mechanism is tentatively proposed for such a three-dimensional hierarchical framework.Due to its attractive structure and componential synergism,MS-Mo2C@NCNS exposes more effective active sites,confers robust structural stability,and shows significant electrocatalytic activity/stability in HER,with a current density of 10 mA cm-2 and an overpotential of only 98 mV in 1 M KOH.Density functional theory calculations point to the synergistic effect of Mo2C HNT and NCNS,leading to enhanced electronic transport and suitable adsorption free energies of H*(ΔGH*)on the surface of electroactive Mo2C.More significantly,the MS-assisted synthetic methodology here provides an enormous perspective for the commercial development of highly active non-noble metal electrocatalysts toward efficient hydrogen evolution.
文摘Precise spatial control of 2D materials is the key capability of engineering their optical,electronic,and mechanical properties.However,growth of novel 2D Mo2C on Cu surface by chemical vapor deposition method was revealed to be seed-induced 2D growth,limiting further synthesis of complex Mo2C spatial structures.In this research,we demonstrate the controlled growth of Mo2C pyramids with numerous morphologies,which are characterized with clear terraces within the structures.The whole evolution for Mo2C pyramids in the coursed of CVD process has been detected,posing significant potential in probing growth mechanism.The formation of the Mo2C pyramids arises from the supersaturation-induced nucleation and concentration-gradient driven diffused growth of a new Mo2C layer on the edged areas of intrinsic ones,as supported by STEM imaging.This work provides a novel Mo2C-based pyramid structure and further reveals a sliding growth mechanism,which could offer impetus for the design of new 3D spatial structures of Mo2C and other 2D materials.
