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
TiO2 doped with C, N and S (TCNS photocatalyst) was prepared by hydrolysis process using titanium iso-propoxide and thiourea. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron micro...TiO2 doped with C, N and S (TCNS photocatalyst) was prepared by hydrolysis process using titanium iso-propoxide and thiourea. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photo electron spectroscopy (XPS), BET surface area, FTIR and diffuse reflectance spectra (DRS). The results showed that the prepared catalysts are anatase type and nanosized par-ticles. The catalysts exhibited stronger absorption in the visible light region with a red shift in the adsorption edge. The photocatalytic activity of TCNS photocatalysts was evaluated by the photocatalytic degradation of isoproturon pesticide in aqueous solution. In the present study the maximum activity was achieved for TCNS5 catalyst at neutral pH with 1 g L-1 catalyst amount and at 1.14 x 10-4 M concentration of the pesticide solution. The TCNS photocatalysts showed higher phtocatalytic activity under solar light irradiation. This is attributed to the synergetic effects of red shift in the absorption edge, higher surface area and the inhibition of charge carrier recombination process.展开更多
Pseudo-capacitive mechanisms can provide higher energy densities than electrical double-layer capacitors while being faster than bulk storage mechanisms.Usually,they suffer from low intrinsic electronic and ion conduc...Pseudo-capacitive mechanisms can provide higher energy densities than electrical double-layer capacitors while being faster than bulk storage mechanisms.Usually,they suffer from low intrinsic electronic and ion conductivities of the active materials.Here,taking advantage of the combination of TiS2 decoration,sulfur doping,and a nanometer-sized structure,as-spun TiO2/C nanofiber composites are developed that enable rapid transport of sodium ions and electrons,and exhibit enhanced pseudo-capacitively dominated capacities.At a scan rate of 0.5 mV s−1,a high pseudo-capacitive contribution(76%of the total storage)is obtained for the S-doped TiS2/TiO2/C electrode(termed as TiS2/S-TiO2/C).Such enhanced pseudocapacitive activity allows rapid chemical kinetics and significantly improves the high-rate sodium storage performance of TiO2.The TiS2/S-TiO2/C composite electrode delivers a high capacity of 114 mAh g−1 at a current density of 5000 mA g−1.The capacity maintains at high level(161 mAh g−1)even after 1500 cycles and is still characterized by 58 mAh g−1 at the extreme condition of 10,000 mA g−1 after 10,000 cycles.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.
文摘TiO2 doped with C, N and S (TCNS photocatalyst) was prepared by hydrolysis process using titanium iso-propoxide and thiourea. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photo electron spectroscopy (XPS), BET surface area, FTIR and diffuse reflectance spectra (DRS). The results showed that the prepared catalysts are anatase type and nanosized par-ticles. The catalysts exhibited stronger absorption in the visible light region with a red shift in the adsorption edge. The photocatalytic activity of TCNS photocatalysts was evaluated by the photocatalytic degradation of isoproturon pesticide in aqueous solution. In the present study the maximum activity was achieved for TCNS5 catalyst at neutral pH with 1 g L-1 catalyst amount and at 1.14 x 10-4 M concentration of the pesticide solution. The TCNS photocatalysts showed higher phtocatalytic activity under solar light irradiation. This is attributed to the synergetic effects of red shift in the absorption edge, higher surface area and the inhibition of charge carrier recombination process.
基金This work was financially supported by National Key R&D Program of China(No.2018YFB0905400)the National Natural Science Foundation of China(Nos.51925207,51872277,and U1910210)+2 种基金Dalian National Laboratory For Clean Energy(DNL)Cooperation Fund,the CAS(DNL180310)the Fundamental Research Funds for the Central Universities(Wk2060140026)Sofja Kovalevskaja award of the Humboldt Society.This project has received funding from the European Union’s Horizon 2020 research and innovation programme under Grant Agreement No.823717-ESTEEM3.
文摘Pseudo-capacitive mechanisms can provide higher energy densities than electrical double-layer capacitors while being faster than bulk storage mechanisms.Usually,they suffer from low intrinsic electronic and ion conductivities of the active materials.Here,taking advantage of the combination of TiS2 decoration,sulfur doping,and a nanometer-sized structure,as-spun TiO2/C nanofiber composites are developed that enable rapid transport of sodium ions and electrons,and exhibit enhanced pseudo-capacitively dominated capacities.At a scan rate of 0.5 mV s−1,a high pseudo-capacitive contribution(76%of the total storage)is obtained for the S-doped TiS2/TiO2/C electrode(termed as TiS2/S-TiO2/C).Such enhanced pseudocapacitive activity allows rapid chemical kinetics and significantly improves the high-rate sodium storage performance of TiO2.The TiS2/S-TiO2/C composite electrode delivers a high capacity of 114 mAh g−1 at a current density of 5000 mA g−1.The capacity maintains at high level(161 mAh g−1)even after 1500 cycles and is still characterized by 58 mAh g−1 at the extreme condition of 10,000 mA g−1 after 10,000 cycles.
