Unraveling the essence of electronic structure effected by d-d orbital coupling of transition metal and methanol oxidation reaction(MOR)performance can fundamentally guide high efficient catalyst design.Herein,density...Unraveling the essence of electronic structure effected by d-d orbital coupling of transition metal and methanol oxidation reaction(MOR)performance can fundamentally guide high efficient catalyst design.Herein,density functional theory(DFT)calculations were performed at first to study the d–d orbital interaction of metallic Pt Pd Cu,revealing that the incorporation of Pd and Cu atoms into Pt system can enhance d-d electron interaction via capturing antibonding orbital electrons of Pt to fill the surrounding Pd and Cu atoms.Under the theoretical guidance,Pt Pd Cu medium entropy alloy aerogels(Pt Pd Cu MEAAs)catalysts have been designed and systematically screened for MOR under acid,alkaline and neutral electrolyte.Furthermore,DFT calculation and in-situ fourier transform infrared spectroscopy analysis indicate that Pt Pd Cu MEAAs follow the direct pathway via formate as the reactive intermediate to be directly oxidized to CO_(2).For practical direct methanol fuel cells(DMFCs),the Pt Pd Cu MEAAs-integrated ultra-thin catalyst layer(4–5μm thickness)as anode exhibits higher peak power density of 35 m W/cm^(2) than commercial Pt/C of 20 m W/cm^(2)(~40μm thickness)under the similar noble metal loading and an impressive stability retention at a 50-m A/cm^(2) constant current for 10 h.This work clearly proves that optimizing the intermediate adsorption capacity via d-d orbital coupling is an effective strategy to design highly efficient catalysts for DMFCs.展开更多
Photocatalytic CO_(2)reduction using atomically dispersed catalysts holds significant potential for addressing global energy and environmental challenges.However,the influence of d-d orbital interactions between metal...Photocatalytic CO_(2)reduction using atomically dispersed catalysts holds significant potential for addressing global energy and environmental challenges.However,the influence of d-d orbital interactions between metal centers and coordinated atoms remains under explored.Herein,nickel phthalocyanine is anchored to the metalexposed crystal face of TiO_(2),forming Ti-Ni-N_(4)coordination.This configuration reveals that the axially coordinated Ti atoms serve as a novel electron channel with electron-donating ability,transferring electrons to the Ni center through d-d coupling.It is found that the dynamic adjustment of bond lengths and d-band centers in Ti-Ni bonding during CO_(2)photoreduction process can effectively modulate the adsorption strengths of the Ni center for different intermediates.This leads to a significant enhancement in the photocatalytic performance for CO_(2)reduction to CO without a sacrificial reagent,achieving an exceptional CO evolution rate of 378.5μmol g^(-1).Furthermore,the d-d coupling mediated by Ti-Ni-N_(4)coordination increases the vacancy formation energy of active sites,preventing the leaching of Ni active centers.This study provides a strategy for the precise design of d-d orbital regulation and resistance to demetallization in photocatalysts for efficient CO_(2)conversion.展开更多
Lead(Pb)plays a significant role in the nuclear industry and is extensively used in radiation shielding,radiation protection,neutron moderation,radiation measurements,and various other critical functions.Consequently,...Lead(Pb)plays a significant role in the nuclear industry and is extensively used in radiation shielding,radiation protection,neutron moderation,radiation measurements,and various other critical functions.Consequently,the measurement and evaluation of Pb nuclear data are highly regarded in nuclear scientific research,emphasizing its crucial role in the field.Using the time-of-flight(ToF)method,the neutron leakage spectra from three^(nat)Pb samples were measured at 60°and 120°based on the neutronics integral experimental facility at the China Institute of Atomic Energy(CIAE).The^(nat)Pb sample sizes were30 cm×30 cm×5 cm,30 cm×30 cm×10 cm,and 30 cm×30 cm×15 cm.Neutron sources were generated by the Cockcroft-Walton accelerator,producing approximately 14.5 MeV and 3.5 MeV neutrons through the T(d,n)^(4)He and D(d,n)^(3)He reactions,respectively.Leakage neutron spectra were also calculated by employing the Monte Carlo code of MCNP-4C,and the nuclear data of Pb isotopes from four libraries:CENDL-3.2,JEFF-3.3,JENDL-5,and ENDF/B-Ⅷ.0 were used individually.By comparing the simulation and experimental results,improvements and deficiencies in the evaluated nuclear data of the Pb isotopes were analyzed.Most of the calculated results were consistent with the experimental results;however,a few areas did not fit well.In the(n,el)energy range,the simulated results from CENDL-3.2 were significantly overestimated;in the(n,inl)D and the(n,inl)C energy regions,the results from CENDL-3.2 and ENDF/B-Ⅷ.0 were significantly overestimated at 120°,and the results from JENDL-5 and JEFF-3.3 are underestimated at 60°in the(n,inl)D energy region.The calculated spectra were analyzed by comparing them with the experimental spectra in terms of the neutron spectrum shape and C/E values.The results indicate that the theoretical simulations,using different data libraries,overestimated or underestimated the measured values in certain energy ranges.Secondary neutron energies and angular distributions in the data files have been presented to explain these discrepancies.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.52073214 and 22075211)Guangxi Natural Science Fund for Distinguished Young Scholars(No.2024GXNSFFA010008)+5 种基金Natural Science Foundation of Shandong Province(Nos.ZR2023MB049 and ZR2021QB129)China Postdoctoral Science Foundation(No.2020M670483)Science Foundation of Weifang University(No.2023BS11)supported by the open research fund of the Laboratory of Xinjiang Native Medicinal and Edible Plant Resources Chemistry at Kashi Universitysupported by the Tianhe Qingsuo Open Research Fund of TSYS in 2022 and NSCC-TJNankai University Large-scale Instrument Experimental Technology R&D Project(No.21NKSYJS09)。
文摘Unraveling the essence of electronic structure effected by d-d orbital coupling of transition metal and methanol oxidation reaction(MOR)performance can fundamentally guide high efficient catalyst design.Herein,density functional theory(DFT)calculations were performed at first to study the d–d orbital interaction of metallic Pt Pd Cu,revealing that the incorporation of Pd and Cu atoms into Pt system can enhance d-d electron interaction via capturing antibonding orbital electrons of Pt to fill the surrounding Pd and Cu atoms.Under the theoretical guidance,Pt Pd Cu medium entropy alloy aerogels(Pt Pd Cu MEAAs)catalysts have been designed and systematically screened for MOR under acid,alkaline and neutral electrolyte.Furthermore,DFT calculation and in-situ fourier transform infrared spectroscopy analysis indicate that Pt Pd Cu MEAAs follow the direct pathway via formate as the reactive intermediate to be directly oxidized to CO_(2).For practical direct methanol fuel cells(DMFCs),the Pt Pd Cu MEAAs-integrated ultra-thin catalyst layer(4–5μm thickness)as anode exhibits higher peak power density of 35 m W/cm^(2) than commercial Pt/C of 20 m W/cm^(2)(~40μm thickness)under the similar noble metal loading and an impressive stability retention at a 50-m A/cm^(2) constant current for 10 h.This work clearly proves that optimizing the intermediate adsorption capacity via d-d orbital coupling is an effective strategy to design highly efficient catalysts for DMFCs.
基金financially supported by the National Natural Science Foundation of China(No.22476042)the Natural Science Foundation of Hena.(No.242300421189)
文摘Photocatalytic CO_(2)reduction using atomically dispersed catalysts holds significant potential for addressing global energy and environmental challenges.However,the influence of d-d orbital interactions between metal centers and coordinated atoms remains under explored.Herein,nickel phthalocyanine is anchored to the metalexposed crystal face of TiO_(2),forming Ti-Ni-N_(4)coordination.This configuration reveals that the axially coordinated Ti atoms serve as a novel electron channel with electron-donating ability,transferring electrons to the Ni center through d-d coupling.It is found that the dynamic adjustment of bond lengths and d-band centers in Ti-Ni bonding during CO_(2)photoreduction process can effectively modulate the adsorption strengths of the Ni center for different intermediates.This leads to a significant enhancement in the photocatalytic performance for CO_(2)reduction to CO without a sacrificial reagent,achieving an exceptional CO evolution rate of 378.5μmol g^(-1).Furthermore,the d-d coupling mediated by Ti-Ni-N_(4)coordination increases the vacancy formation energy of active sites,preventing the leaching of Ni active centers.This study provides a strategy for the precise design of d-d orbital regulation and resistance to demetallization in photocatalysts for efficient CO_(2)conversion.
基金supported by the National Natural Science Foundation of China(Nos.11775311 and U2067205)the Stable Support Basic Research Program Grant(BJ010261223282)the Research and Development Project of China National Nuclear Corporation。
文摘Lead(Pb)plays a significant role in the nuclear industry and is extensively used in radiation shielding,radiation protection,neutron moderation,radiation measurements,and various other critical functions.Consequently,the measurement and evaluation of Pb nuclear data are highly regarded in nuclear scientific research,emphasizing its crucial role in the field.Using the time-of-flight(ToF)method,the neutron leakage spectra from three^(nat)Pb samples were measured at 60°and 120°based on the neutronics integral experimental facility at the China Institute of Atomic Energy(CIAE).The^(nat)Pb sample sizes were30 cm×30 cm×5 cm,30 cm×30 cm×10 cm,and 30 cm×30 cm×15 cm.Neutron sources were generated by the Cockcroft-Walton accelerator,producing approximately 14.5 MeV and 3.5 MeV neutrons through the T(d,n)^(4)He and D(d,n)^(3)He reactions,respectively.Leakage neutron spectra were also calculated by employing the Monte Carlo code of MCNP-4C,and the nuclear data of Pb isotopes from four libraries:CENDL-3.2,JEFF-3.3,JENDL-5,and ENDF/B-Ⅷ.0 were used individually.By comparing the simulation and experimental results,improvements and deficiencies in the evaluated nuclear data of the Pb isotopes were analyzed.Most of the calculated results were consistent with the experimental results;however,a few areas did not fit well.In the(n,el)energy range,the simulated results from CENDL-3.2 were significantly overestimated;in the(n,inl)D and the(n,inl)C energy regions,the results from CENDL-3.2 and ENDF/B-Ⅷ.0 were significantly overestimated at 120°,and the results from JENDL-5 and JEFF-3.3 are underestimated at 60°in the(n,inl)D energy region.The calculated spectra were analyzed by comparing them with the experimental spectra in terms of the neutron spectrum shape and C/E values.The results indicate that the theoretical simulations,using different data libraries,overestimated or underestimated the measured values in certain energy ranges.Secondary neutron energies and angular distributions in the data files have been presented to explain these discrepancies.
