The increasing prevalence of antibiotic norfloxacin(NOR)residues in aquatic environments necessitates the research of high-efficiency and eco-friendly photocatalysts for their degradation.In this study,plasma-treated{...The increasing prevalence of antibiotic norfloxacin(NOR)residues in aquatic environments necessitates the research of high-efficiency and eco-friendly photocatalysts for their degradation.In this study,plasma-treated{010}-faceted BiVO_(4)(denoted as BiVO_(4)-010-P)with abundant oxygen vacancies(V_(O))and plasmonic Bi nanoparticles was strategically employed to achieve efficient NOR degradation via peroxymonosulfate(PMS)activation.Compared with pristine BiVO_(4),BiVO_(4)-010-P exhibits significantly enhanced photocatalytic PMS activation performance,achieving approximately 95%NOR removal within 80 min under white LED irradiation.Experimental and theoretical calculations prove that metallic Bi particles not only enhanced its light-absorption capacity,generating more hot electrons,but also accelerate electrons transfer from metallic Bi to BiVO_(4)-010-V_(O).Meanwhile,the generation V_(O) not only enhances PMS adsorption,but also facilitates charge transfer between BiVO_(4)-010-V_(O) and PMS.These synergistic effects collectively contribute to enhanced photocatalytic activity.This study proposes an innovative surface engineering strategy for designing efficient photocatalyst materials for addressing antibiotic pollutants in wastewater treatment systems.展开更多
Overcoming kinetic limitations in the acidic oxygen reduction reaction(ORR)demands Pt-based catalysts with optimized surface adsorption.Herein,we engineer hierarchical PtPd dendrite nanocrystals(PtPd NDs)featuring pre...Overcoming kinetic limitations in the acidic oxygen reduction reaction(ORR)demands Pt-based catalysts with optimized surface adsorption.Herein,we engineer hierarchical PtPd dendrite nanocrystals(PtPd NDs)featuring precisely tailored asymmetric sites and high-index facets(HIFs)to overcome the kinetic limitations in acidic media.Controlled Pd incorporation disrupts symmetry of the single-oriented crystal plane,generating inhomogeneous strain and promoting HIFs exposure.This synergistic structural engineering optimizes the adsorption/desorption of oxygen-containing intermediates,significantly accelerating ORR kinetics.Consequently,PtPd NDs deliver exceptional mass activity(MA=1.37 A mg_(Pt)^(-1),11.42 times higher than Pt/C)and remarkable stability(83.9%MA retention after durability testing).In H_(2)-Air fuel cells,PtPd NDs also achieve higher peak power density versus Pt/C cathodes.In situ synchrotron radiation infrared spectroscopy and theoretical studies reveal that the synergistic effect between asymmetric sites and HIFs stimulates the strain field and causes a downward shift in the d-band center,thereby lowering the*OOH formation barrier and weakening intermediate adsorption,directly boosting the ORR performance.This work underscores the critical role of facet and site engineering in designing high-performance fuel cell electrocatalysts.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
The hydrogenation of carbon dioxide to produce high-value fuels such as ethanol is currently a research hotspot,but addressing the low selectivity for ethanol remains a challenge.Herein,morphologycontrolled CeO_(2) wi...The hydrogenation of carbon dioxide to produce high-value fuels such as ethanol is currently a research hotspot,but addressing the low selectivity for ethanol remains a challenge.Herein,morphologycontrolled CeO_(2) with different exposed crystal facets,including nanorods(220),nanocubes(200)and nanoplatelets(111),were prepared and impregnated with rhodium(Rh)to obtain Rh/CeO_(2) catalysts,and then the catalytic performance of CO_(2) hydrogenation was investigated.Rh/CeO_(2)-r(nanorods)exhibits high efficacy for CO_(2) hydrogenation to ethanol,giving a high ethanol selectivity of 20.9%with a moderate CO_(2) conversion of 11.2%,and the one-pass ethanol productivity reaches 69.2 mmol/(gRh·h).Characterization results reveal that tuning the exposed crystal facets of the CeO_(2) can tailor the interaction between Rh and CeO_(2),and adjust the chemical state of the Rh species.Due to the abundant oxygen vacancies occupied on the exposed(220)facets of CeO_(2) nanorods,multi-level interactions arise between Rh and CeO_(2)-r,and produce more content of Rh^(+)species.This interface facilitates the transformation of carbonate species into HCOO^(*)and CO^(*)simultaneously,finally boosting the ethanol formation by the C-C coupling reaction.展开更多
Cu electrocatalysts have been demonstrated to have unique ability to reduce CO_(2)to various high value-added C_(2) products like ethylene and alcohols.However,realizing high selectivity of C_(2) products are still a ...Cu electrocatalysts have been demonstrated to have unique ability to reduce CO_(2)to various high value-added C_(2) products like ethylene and alcohols.However,realizing high selectivity of C_(2) products are still a main challenge due to complex CO_(2)electroreduction pathways and small opportunity of C-C coupling reactions.Here,we found the origin of enhanced CO_(2)electroreduction reaction activity and product selectivity towards C_(2) products and C-C coupling mechanism at halogen atoms-adsorbed Cu/H_(2)O interfaces,the corresponding CO_(2)electroreduction evolution mechanisms at the halogen atoms-modified Cu/H_(2)O interfaces are systematically studied via theoretical modeling and calculations.The calculated results indicate that halide anions modifications are beneficial to CO dimerization into OCCO dimer,especially Cl^(-)-adsorbed Cu(111)/H_(2)O interface has the optimum activity and selectivity towards OCCO dimer,subsequent Cl-adsorbed Cu(111)/H_(2)O interface can selectively reduce CO_(2)into C_(2)H_(4) product.The function relationship between adsorption free energy of Cl atom and electrode potential explain why the adsorption of Cl^(-)can enhance selectivity of C_(2)H_(4) product.The determinations of onset potentials indicate that electroreduction pathways of CO_(2)towards C_(2)H_(4) product are facile to take place and further explain the origin of the significantly enhanced CO production activity and C_(2)H_(4) product selectivity.This work on selective realization of CO_(2)electroreduction towards C_(2)H_(4) product via Cl^(-)-modified Cu(111)/H_(2)O interface provide a theoretical guideline for how to selectively realize other high value-added C_(2) products.展开更多
A series of Ag2–xO/FTO-i electrodes(where i denotes the current density during the electrodeposition, and i = 0.5, 1, 2, 3, 4, or 7) was fabricated in 0.1 M K2B4O7 electrolyte containing Ag+ ions by galvanostatic ele...A series of Ag2–xO/FTO-i electrodes(where i denotes the current density during the electrodeposition, and i = 0.5, 1, 2, 3, 4, or 7) was fabricated in 0.1 M K2B4O7 electrolyte containing Ag+ ions by galvanostatic electrocrystallization. The electrode composition and morphology were characterized using X-ray powder diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy. The results reveal that the electrode films consist of Ag2O, but some of the Ag+ ions on the {111} crystal facets are oxidized into Ag2+ ions. Furthermore, the Ag2–xO/FTO-1 electrode shows a triangular slice shape of a parallel matrix with a larger exposed area of {111} crystal facets than other Ag2–xO/FTO-i(i = 0.5, 2, 3, 4, or 7) electrodes. Electrocatalytic experiments prove that the Ag2–xO/FTO-1 electrode produces the highest oxidative current density, has an overpotential of 417 m V at 10 m A cm–2, and has a Tafel slope of 47 m V dec–1 in 0.1 M K2B4O7. Electrochemical impedance spectra indicate that Ag2–xO/FTO-1 electrodes have the best ability for charge transfer. In addition, in the I-t test over 10 h, the current density decreased 4%. Fortunately, both O–O and Ag2+ species were detected after electrocatalysis and a possible mechanism for the oxygen evolution reaction is proposed in which the formation of Ag2+ and O–O species on {111} facets plays a critical role.展开更多
基金support from the National Natural Science Foundation of China(52102362)Shandong Provincial Natural Science Foundation(ZR2021QB022)+2 种基金China Postdoctoral Science Foundation(2024M761557)Taishan Scholars Program of Shandong Province(tsqn202408162,ts201712030,tstp20230665)Technology Support Program for Youth Innovation Team of Shandong Universities(2023KJ225,2024KJH144).
文摘The increasing prevalence of antibiotic norfloxacin(NOR)residues in aquatic environments necessitates the research of high-efficiency and eco-friendly photocatalysts for their degradation.In this study,plasma-treated{010}-faceted BiVO_(4)(denoted as BiVO_(4)-010-P)with abundant oxygen vacancies(V_(O))and plasmonic Bi nanoparticles was strategically employed to achieve efficient NOR degradation via peroxymonosulfate(PMS)activation.Compared with pristine BiVO_(4),BiVO_(4)-010-P exhibits significantly enhanced photocatalytic PMS activation performance,achieving approximately 95%NOR removal within 80 min under white LED irradiation.Experimental and theoretical calculations prove that metallic Bi particles not only enhanced its light-absorption capacity,generating more hot electrons,but also accelerate electrons transfer from metallic Bi to BiVO_(4)-010-V_(O).Meanwhile,the generation V_(O) not only enhances PMS adsorption,but also facilitates charge transfer between BiVO_(4)-010-V_(O) and PMS.These synergistic effects collectively contribute to enhanced photocatalytic activity.This study proposes an innovative surface engineering strategy for designing efficient photocatalyst materials for addressing antibiotic pollutants in wastewater treatment systems.
基金supported by Yunnan Province Key Research and Development Program(202503AA080007)the Open Project of Yunnan Precious Metals Laboratory Co.,Ltd.(YPML-20240502051and YPML-2023050204)+1 种基金the National Natural Science Foundation of China(12405377)the Science and Technology Planning Project of Yunnan Province(202302AH360001)。
文摘Overcoming kinetic limitations in the acidic oxygen reduction reaction(ORR)demands Pt-based catalysts with optimized surface adsorption.Herein,we engineer hierarchical PtPd dendrite nanocrystals(PtPd NDs)featuring precisely tailored asymmetric sites and high-index facets(HIFs)to overcome the kinetic limitations in acidic media.Controlled Pd incorporation disrupts symmetry of the single-oriented crystal plane,generating inhomogeneous strain and promoting HIFs exposure.This synergistic structural engineering optimizes the adsorption/desorption of oxygen-containing intermediates,significantly accelerating ORR kinetics.Consequently,PtPd NDs deliver exceptional mass activity(MA=1.37 A mg_(Pt)^(-1),11.42 times higher than Pt/C)and remarkable stability(83.9%MA retention after durability testing).In H_(2)-Air fuel cells,PtPd NDs also achieve higher peak power density versus Pt/C cathodes.In situ synchrotron radiation infrared spectroscopy and theoretical studies reveal that the synergistic effect between asymmetric sites and HIFs stimulates the strain field and causes a downward shift in the d-band center,thereby lowering the*OOH formation barrier and weakening intermediate adsorption,directly boosting the ORR performance.This work underscores the critical role of facet and site engineering in designing high-performance fuel cell electrocatalysts.
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.
基金Project supported by the Shanghai Local Capacity Building Project(23010504600)。
文摘The hydrogenation of carbon dioxide to produce high-value fuels such as ethanol is currently a research hotspot,but addressing the low selectivity for ethanol remains a challenge.Herein,morphologycontrolled CeO_(2) with different exposed crystal facets,including nanorods(220),nanocubes(200)and nanoplatelets(111),were prepared and impregnated with rhodium(Rh)to obtain Rh/CeO_(2) catalysts,and then the catalytic performance of CO_(2) hydrogenation was investigated.Rh/CeO_(2)-r(nanorods)exhibits high efficacy for CO_(2) hydrogenation to ethanol,giving a high ethanol selectivity of 20.9%with a moderate CO_(2) conversion of 11.2%,and the one-pass ethanol productivity reaches 69.2 mmol/(gRh·h).Characterization results reveal that tuning the exposed crystal facets of the CeO_(2) can tailor the interaction between Rh and CeO_(2),and adjust the chemical state of the Rh species.Due to the abundant oxygen vacancies occupied on the exposed(220)facets of CeO_(2) nanorods,multi-level interactions arise between Rh and CeO_(2)-r,and produce more content of Rh^(+)species.This interface facilitates the transformation of carbonate species into HCOO^(*)and CO^(*)simultaneously,finally boosting the ethanol formation by the C-C coupling reaction.
基金supported by the Natural Science Foundation of Hunan Province(No.2025JJ50059)Key Program of Hunan University of Arts and Science(No.23ZZ03)Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province and National Natural Science Foundation of China(No.21303048).
文摘Cu electrocatalysts have been demonstrated to have unique ability to reduce CO_(2)to various high value-added C_(2) products like ethylene and alcohols.However,realizing high selectivity of C_(2) products are still a main challenge due to complex CO_(2)electroreduction pathways and small opportunity of C-C coupling reactions.Here,we found the origin of enhanced CO_(2)electroreduction reaction activity and product selectivity towards C_(2) products and C-C coupling mechanism at halogen atoms-adsorbed Cu/H_(2)O interfaces,the corresponding CO_(2)electroreduction evolution mechanisms at the halogen atoms-modified Cu/H_(2)O interfaces are systematically studied via theoretical modeling and calculations.The calculated results indicate that halide anions modifications are beneficial to CO dimerization into OCCO dimer,especially Cl^(-)-adsorbed Cu(111)/H_(2)O interface has the optimum activity and selectivity towards OCCO dimer,subsequent Cl-adsorbed Cu(111)/H_(2)O interface can selectively reduce CO_(2)into C_(2)H_(4) product.The function relationship between adsorption free energy of Cl atom and electrode potential explain why the adsorption of Cl^(-)can enhance selectivity of C_(2)H_(4) product.The determinations of onset potentials indicate that electroreduction pathways of CO_(2)towards C_(2)H_(4) product are facile to take place and further explain the origin of the significantly enhanced CO production activity and C_(2)H_(4) product selectivity.This work on selective realization of CO_(2)electroreduction towards C_(2)H_(4) product via Cl^(-)-modified Cu(111)/H_(2)O interface provide a theoretical guideline for how to selectively realize other high value-added C_(2) products.
文摘A series of Ag2–xO/FTO-i electrodes(where i denotes the current density during the electrodeposition, and i = 0.5, 1, 2, 3, 4, or 7) was fabricated in 0.1 M K2B4O7 electrolyte containing Ag+ ions by galvanostatic electrocrystallization. The electrode composition and morphology were characterized using X-ray powder diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy. The results reveal that the electrode films consist of Ag2O, but some of the Ag+ ions on the {111} crystal facets are oxidized into Ag2+ ions. Furthermore, the Ag2–xO/FTO-1 electrode shows a triangular slice shape of a parallel matrix with a larger exposed area of {111} crystal facets than other Ag2–xO/FTO-i(i = 0.5, 2, 3, 4, or 7) electrodes. Electrocatalytic experiments prove that the Ag2–xO/FTO-1 electrode produces the highest oxidative current density, has an overpotential of 417 m V at 10 m A cm–2, and has a Tafel slope of 47 m V dec–1 in 0.1 M K2B4O7. Electrochemical impedance spectra indicate that Ag2–xO/FTO-1 electrodes have the best ability for charge transfer. In addition, in the I-t test over 10 h, the current density decreased 4%. Fortunately, both O–O and Ag2+ species were detected after electrocatalysis and a possible mechanism for the oxygen evolution reaction is proposed in which the formation of Ag2+ and O–O species on {111} facets plays a critical role.
