To simultaneously improve the critical factors in photocatalytic H_(2)production,the population of active photogenerated electrons,the adsorption and activation of H_(2)O molecules,and the surface dehydrogenation effi...To simultaneously improve the critical factors in photocatalytic H_(2)production,the population of active photogenerated electrons,the adsorption and activation of H_(2)O molecules,and the surface dehydrogenation efficiency,we propose a synergistic strategy for TiO_(2)modification by combining transition metal(TM)doping and N-doped carbon(N-C)coating.The targeted Cr-TiO_(2)@N-C heterojunction exhibits dramatically enhanced H_(2)production under blue light irradiation,contrasting sharply with a negligible production by pristine TiO_(2).Comprehensive structural characterization and theoretical calculations confirm the uniform substitution of Cr into the TiO_(2)lattice,promoting the formation of adjacent oxygen vacancies(VO).The synergistic effect of Cr doping and VO extends the light absorption range into the visible region.The coated N-C layer facilitates the efficient separation of photogenerated charge carriers,boosting the population of active electrons.Critically,the combined action of VO and N-C layer enhances the adsorption and activation of H_(2)O molecules while effectively improving the subsequent surface dehydrogenation efficiency.Significantly,this strategy demonstrates broad universality:Analogous TM-TiO_(2)@N-C heterojunctions(TM=Mn,Co,Ni,Cu,and Zn)synthesized via the same approach all show substantially improved H_(2)production performance over pristine TiO_(2).展开更多
Micro-sized anatase TiO_(2) displays inferior capacity as cathode material for magnesium ion batteries because of the higher diffusion energy barrier of Mg^(2+)in anatase TiO_(2) lattice.Herein,we report that nanosize...Micro-sized anatase TiO_(2) displays inferior capacity as cathode material for magnesium ion batteries because of the higher diffusion energy barrier of Mg^(2+)in anatase TiO_(2) lattice.Herein,we report that nanosized anatase TiO_(2) exposed(001)facet doubles the capacity compared to the micro-sized sample ascribed to the interfacial Mg^(2+)ion storage.First-principles calculations reveal that the diffusion energy barrier of Mg^(2+)on the(001)facet is significantly lower than those in the bulk phase and on(100)facet,and the adsorption energy of Mg^(2+)on the(001)facet is also considerably lower than that on(100)facet,which guarantees superior interfacial Mg^(2+)storage of(001)facet.Moreover,anatase TiO_(2) exposed(001)facet displays a significantly higher capacity of 312.9 mAh g^(−1) in Mg-Li dual-salt electrolyte compared to 234.3 mAh g^(−1) in Li salt electrolyte.The adsorption energies of Mg^(2+)on(001)facet are much lower than the adsorption energies of Li+on(001)facet,implying that the Mg^(2+)ion interfacial storage is more favorable.These results highlight that controlling the crystal facet of the nanocrystals effectively enhances the interfacial storage of multivalent ions.This work offers valuable guidance for the rational design of high-capacity storage systems.展开更多
基金supported by the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.24KJA150003)the Xuzhou Key Research and Development Program(Social Development)(No.KC23298)+1 种基金the National Natural Science Foundation of China(No.22271122)Basic Research Program of Jiangsu(No.BK20253049).
文摘To simultaneously improve the critical factors in photocatalytic H_(2)production,the population of active photogenerated electrons,the adsorption and activation of H_(2)O molecules,and the surface dehydrogenation efficiency,we propose a synergistic strategy for TiO_(2)modification by combining transition metal(TM)doping and N-doped carbon(N-C)coating.The targeted Cr-TiO_(2)@N-C heterojunction exhibits dramatically enhanced H_(2)production under blue light irradiation,contrasting sharply with a negligible production by pristine TiO_(2).Comprehensive structural characterization and theoretical calculations confirm the uniform substitution of Cr into the TiO_(2)lattice,promoting the formation of adjacent oxygen vacancies(VO).The synergistic effect of Cr doping and VO extends the light absorption range into the visible region.The coated N-C layer facilitates the efficient separation of photogenerated charge carriers,boosting the population of active electrons.Critically,the combined action of VO and N-C layer enhances the adsorption and activation of H_(2)O molecules while effectively improving the subsequent surface dehydrogenation efficiency.Significantly,this strategy demonstrates broad universality:Analogous TM-TiO_(2)@N-C heterojunctions(TM=Mn,Co,Ni,Cu,and Zn)synthesized via the same approach all show substantially improved H_(2)production performance over pristine TiO_(2).
基金supported by the National Key R&D Program of China(No.2023YFB3809500)the Fundamental Research Funds for the Central Universities(No.2024CDJXY003)+1 种基金the Venture&Innovation Support Program for Chongqing Overseas Returnees(cx2023087)The Chongqing Technology Innovation and Application Development Project(No.2024TIAD-KPX0003).
文摘Micro-sized anatase TiO_(2) displays inferior capacity as cathode material for magnesium ion batteries because of the higher diffusion energy barrier of Mg^(2+)in anatase TiO_(2) lattice.Herein,we report that nanosized anatase TiO_(2) exposed(001)facet doubles the capacity compared to the micro-sized sample ascribed to the interfacial Mg^(2+)ion storage.First-principles calculations reveal that the diffusion energy barrier of Mg^(2+)on the(001)facet is significantly lower than those in the bulk phase and on(100)facet,and the adsorption energy of Mg^(2+)on the(001)facet is also considerably lower than that on(100)facet,which guarantees superior interfacial Mg^(2+)storage of(001)facet.Moreover,anatase TiO_(2) exposed(001)facet displays a significantly higher capacity of 312.9 mAh g^(−1) in Mg-Li dual-salt electrolyte compared to 234.3 mAh g^(−1) in Li salt electrolyte.The adsorption energies of Mg^(2+)on(001)facet are much lower than the adsorption energies of Li+on(001)facet,implying that the Mg^(2+)ion interfacial storage is more favorable.These results highlight that controlling the crystal facet of the nanocrystals effectively enhances the interfacial storage of multivalent ions.This work offers valuable guidance for the rational design of high-capacity storage systems.
