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
以三聚氰胺苯甲酸盐为碳源和氮源、以三聚氰胺磷钼酸盐为钼源、磷源和氮源,采用程序升温的方法制备了系列N,P掺杂型C@Mo_2C催化剂。采用XRD、SEM、TEM和XPS等对催化剂的结构、形貌和表面特性进行了表征,研究了三聚氰胺苯甲酸盐中n(三聚...以三聚氰胺苯甲酸盐为碳源和氮源、以三聚氰胺磷钼酸盐为钼源、磷源和氮源,采用程序升温的方法制备了系列N,P掺杂型C@Mo_2C催化剂。采用XRD、SEM、TEM和XPS等对催化剂的结构、形貌和表面特性进行了表征,研究了三聚氰胺苯甲酸盐中n(三聚氰胺)/n(苯甲酸)、前驱体中n(C)/n(Mo)等因素对所制备催化剂的结构及其在二氧化碳加氢反应中催化性能的影响。在反应温度为220℃、反应压力为3.0 MPa、空速为3 600 m L/(g·h)的条件下,在N,P掺杂型C@Mo_2C的催化作用下,CO_2转化率可以达到12.2%,此时产物中CH_3OH的选择性达到52.2%。展开更多
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
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
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
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
Tattoo electronics has attracted intensive interest in recent years due to its comfortable wearing and imperceivable sensing,and has been broadly applied in wearable healthcare and human-machine interface.However,the ...Tattoo electronics has attracted intensive interest in recent years due to its comfortable wearing and imperceivable sensing,and has been broadly applied in wearable healthcare and human-machine interface.However,the tattoo electrodes are mostly composed of metal films and conductive polymers.Two-dimensional(2D)materials,which are superior in conductivity and stability,are barely studied for electronic tattoos.Herein,we reported a novel electronic tattoo based on large-area Mo_(2)C film grown by chemical vapor deposition(CVD),and applied it to accurately and imperceivably acquire on-body electrophysiological signals and interface with robotics.High-quality Mo_(2)C film was obtained via optimizing the distribution of gas flow during CVD growth.According to the finite element simulation(FES),bottom surface of Cu foil covers more stable gas flow than the top surface,thus leading to more uniform Mo_(2)C film.The resulting Mo_(2)C film was transferred onto tattoo paper,showing a total thickness of~3μm,sheet resistance of 60-150Ω/sq,and skin-electrode impedance of~5×10^(5)Ω.Such thin Mo_(2)C electronic tattoo(MCET in short)can form conformal contact with skin and accurately record electrophysiological signals,including electromyography(EMG),electrocardiogram(ECG),and electrooculogram(EOG).These body signals collected by MCET can not only reflect the health status but also be transformed to control the robotics for human-machine interface.展开更多
Herein,we first report one-step synthesis of uniform Mo2 C microflowers(MCMFs)from low-cost precursors via industrialized solid-state strategy.With fine optimization in precursor ratio and pyrolysis temperatures,the a...Herein,we first report one-step synthesis of uniform Mo2 C microflowers(MCMFs)from low-cost precursors via industrialized solid-state strategy.With fine optimization in precursor ratio and pyrolysis temperatures,the as-fabricated MCMFs are assembled well with interconnected single-crystalline nanosheet subunits.More encouragingly,the resultant MCMFs are further highlighted as a competitive anode with robust and long-duration lithium-storage behaviors towards high-performance Li-ion batteries.展开更多
近日,华西医院疾病系统遗传研究院/疾病分子网络前沿科学中心/蛋白组学-代谢组学平台龚萌副研究员团队与麻醉手术中心/线粒体与代谢研究室李涛研究员团队合作,在Biomaterials (IF:15.304)发表文章"Integrated metabolomics reveale...近日,华西医院疾病系统遗传研究院/疾病分子网络前沿科学中心/蛋白组学-代谢组学平台龚萌副研究员团队与麻醉手术中心/线粒体与代谢研究室李涛研究员团队合作,在Biomaterials (IF:15.304)发表文章"Integrated metabolomics revealed the fibromyalgia-alleviation effect of Mo2C nanozyme through regulated homeostasis of oxidative stress and energy metabolism",首次发现Mo2C纳米酶对利血平诱导产生的纤维肌痛具有治疗作用,并首次借助综合代谢组学技术揭示了纤维肌痛治疗过程中的能量代谢分子机制.该研究认为Mo2C纳米酶具有作为纤维肌痛治疗药物的潜力,为纤维肌痛的临床治疗提供了新思路.展开更多
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.
文摘以三聚氰胺苯甲酸盐为碳源和氮源、以三聚氰胺磷钼酸盐为钼源、磷源和氮源,采用程序升温的方法制备了系列N,P掺杂型C@Mo_2C催化剂。采用XRD、SEM、TEM和XPS等对催化剂的结构、形貌和表面特性进行了表征,研究了三聚氰胺苯甲酸盐中n(三聚氰胺)/n(苯甲酸)、前驱体中n(C)/n(Mo)等因素对所制备催化剂的结构及其在二氧化碳加氢反应中催化性能的影响。在反应温度为220℃、反应压力为3.0 MPa、空速为3 600 m L/(g·h)的条件下,在N,P掺杂型C@Mo_2C的催化作用下,CO_2转化率可以达到12.2%,此时产物中CH_3OH的选择性达到52.2%。
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(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.
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.
基金supported by the National Natural Science Foundation of China(Nos.21903007,22072006,and 22275022)Young Thousand Talents Program(No.110532103)+2 种基金Beijing Normal University Startup funding(No.312232102)Beijing Municipal Science&Technology Commission(No.Z191100000819002)the Fundamental Research Funds for the Central Universities(No.310421109).
文摘Tattoo electronics has attracted intensive interest in recent years due to its comfortable wearing and imperceivable sensing,and has been broadly applied in wearable healthcare and human-machine interface.However,the tattoo electrodes are mostly composed of metal films and conductive polymers.Two-dimensional(2D)materials,which are superior in conductivity and stability,are barely studied for electronic tattoos.Herein,we reported a novel electronic tattoo based on large-area Mo_(2)C film grown by chemical vapor deposition(CVD),and applied it to accurately and imperceivably acquire on-body electrophysiological signals and interface with robotics.High-quality Mo_(2)C film was obtained via optimizing the distribution of gas flow during CVD growth.According to the finite element simulation(FES),bottom surface of Cu foil covers more stable gas flow than the top surface,thus leading to more uniform Mo_(2)C film.The resulting Mo_(2)C film was transferred onto tattoo paper,showing a total thickness of~3μm,sheet resistance of 60-150Ω/sq,and skin-electrode impedance of~5×10^(5)Ω.Such thin Mo_(2)C electronic tattoo(MCET in short)can form conformal contact with skin and accurately record electrophysiological signals,including electromyography(EMG),electrocardiogram(ECG),and electrooculogram(EOG).These body signals collected by MCET can not only reflect the health status but also be transformed to control the robotics for human-machine interface.
基金financial support from National Natural Science Foundation of China(Nos.51772127,51772131,51802119)Taishan Scholars(No.ts201712050)Major Program of Shandong Province Natural Science Foundation(No.ZR2018ZB0317)。
文摘Herein,we first report one-step synthesis of uniform Mo2 C microflowers(MCMFs)from low-cost precursors via industrialized solid-state strategy.With fine optimization in precursor ratio and pyrolysis temperatures,the as-fabricated MCMFs are assembled well with interconnected single-crystalline nanosheet subunits.More encouragingly,the resultant MCMFs are further highlighted as a competitive anode with robust and long-duration lithium-storage behaviors towards high-performance Li-ion batteries.
文摘近日,华西医院疾病系统遗传研究院/疾病分子网络前沿科学中心/蛋白组学-代谢组学平台龚萌副研究员团队与麻醉手术中心/线粒体与代谢研究室李涛研究员团队合作,在Biomaterials (IF:15.304)发表文章"Integrated metabolomics revealed the fibromyalgia-alleviation effect of Mo2C nanozyme through regulated homeostasis of oxidative stress and energy metabolism",首次发现Mo2C纳米酶对利血平诱导产生的纤维肌痛具有治疗作用,并首次借助综合代谢组学技术揭示了纤维肌痛治疗过程中的能量代谢分子机制.该研究认为Mo2C纳米酶具有作为纤维肌痛治疗药物的潜力,为纤维肌痛的临床治疗提供了新思路.