Alkali halide clusters are interesting model systems that can provide information about how crystal properties evolve. To study these properties, a high-resolution atmospheric pressure inlet time-of-flight mass spectr...Alkali halide clusters are interesting model systems that can provide information about how crystal properties evolve. To study these properties, a high-resolution atmospheric pressure inlet time-of-flight mass spectrometry （APi-TOF-MS） study of the sequential sodium halides series, C1-（NaC1）n and Br-（NaBr）m, has been reported, and the viability of the APi-TOF- MS equipped with an electrospray ionization source in determining cluster compositions has been demonstrated. The isotopic patterns were well resolved, as n=4 and 7 were determined to be the magic numbers for C1-（NaC1）n clusters, which were particularly abundant in the mass spectra. A global minimum search based on density functional theory enabled basin hopping yield the most stable structures for the mentioned series. The structures exhibit several distinct motifs which can be roughly categorized as linear chain, rock salt, and hexag- onal ring. This work provides an effective way to discover and elucidate the nonstoichiometry sodium halide clusters. These clusters possess very high vertical detachment energies and are generally called as superhalogens, which play important roles in chemistry because they are widely used in the synthesis of new classes of charge-transfer salts.展开更多
Despite the intense research efforts directed to electrocatalytic nitrogen reduction reaction(eNRR),the NH_(3) yield and selectivity are still not up to the standard of practical application.Here,high-entropy perovski...Despite the intense research efforts directed to electrocatalytic nitrogen reduction reaction(eNRR),the NH_(3) yield and selectivity are still not up to the standard of practical application.Here,high-entropy perovskite oxides with composition Bax(FeCoNiZrY)_(0.2)O_(3−δ)(Bx(FCNZY)_(0.2)(x=0.9,1)are reported as eNRR catalysts.The eNRR activity of high-entropy perovskite oxide is enhanced by changing the nonstoichiometric metal elements at the A-site,thus generating additional oxygen vacancies.The NH_(3) yield and Faraday efficiency for B_(0.9)(FCNZY)_(0.2) are 1.51 and 1.95 times higher than those for B(FCNZY)_(0.2),respectively.The d-band center theory is used to theoretically predict the catalytically active center at the B-site,and as a result,nickel was identified as the catalytic site.The free energy values of the intermediate states in the optimal distal pathway show that the third protonation step(*NNH_(2)→*NNH_(3))is the rate-determining step and that the increase in oxygen vacancies in the high-entropy perovskite contributes to nitrogen adsorption and reduction.This work provides a framework for applying high-entropy structures with active site diversity for electrocatalytic nitrogen fixation.展开更多
Material functionalities strongly depend on the stoichiometry,crystal structure,and homogeneity.Here we demonstrate an approach of amorphous nonstoichiometric inhomogeneous oxides to realize tunable ferromagnetism and...Material functionalities strongly depend on the stoichiometry,crystal structure,and homogeneity.Here we demonstrate an approach of amorphous nonstoichiometric inhomogeneous oxides to realize tunable ferromagnetism and electrical transport at room temperature.In order to verify the origin of the ferromagnetism,we employed a series of structural,chemical,and electronic state characterizations.Combined with electron microscopy and transport measurements,synchrotron-based grazing incident wide angle X-ray scattering,soft X-ray absorption and circular dichroism clearly reveal that the roomtemperature ferromagnetism originates from the In0.23Co0.77O1-v,amorphous phase with a large tunable range of oxygen vacancies.The room-temperature ferromagnetism is tunable from a high saturation magnetization of 500 emu cm-3 to below 25 emu cm-3,with the evolving electrical resistivity from5×103μΩ cm to above 2.5×105 μΩ cm.Inhomogeneous nano-crystallization emerges with decreasing oxygen vacancies,driving the system towards non-ferromagnetism and insulating regime.Our work unfolds the novel functionalities of amorphous nonstoichiometric inhomogeneous oxides,which opens up new opportunities for developing spintronic materials with superior magnetic and transport properties.展开更多
文摘Alkali halide clusters are interesting model systems that can provide information about how crystal properties evolve. To study these properties, a high-resolution atmospheric pressure inlet time-of-flight mass spectrometry （APi-TOF-MS） study of the sequential sodium halides series, C1-（NaC1）n and Br-（NaBr）m, has been reported, and the viability of the APi-TOF- MS equipped with an electrospray ionization source in determining cluster compositions has been demonstrated. The isotopic patterns were well resolved, as n=4 and 7 were determined to be the magic numbers for C1-（NaC1）n clusters, which were particularly abundant in the mass spectra. A global minimum search based on density functional theory enabled basin hopping yield the most stable structures for the mentioned series. The structures exhibit several distinct motifs which can be roughly categorized as linear chain, rock salt, and hexag- onal ring. This work provides an effective way to discover and elucidate the nonstoichiometry sodium halide clusters. These clusters possess very high vertical detachment energies and are generally called as superhalogens, which play important roles in chemistry because they are widely used in the synthesis of new classes of charge-transfer salts.
基金supported by the National Natural Science Foundation of China (52161135302, 21674019, and 51801075)the Research Foundation Flanders (G0F2322N)+8 种基金Shanghai Scientific and Technological Innovation Project (18JC1410600)the Program of the Shanghai Academic Research Leader (17XD1400100)the financial support from the Flemish Government through the Moonshot cSBO project P2C (HBC.2019.0108)the Long-term Structural Funding (Methusalem CASAS2, Meth/15/04)Interne Fondsen KU Leuven through project C3/20/067the support from the Research Foundation-Flanders (FWO) in the form of a doctoral fellowship (1SA3321N)the financial support from China Scholarship Council in the form of a visiting Ph.D. Student (File No. 202106790090)the LvLiang Cloud Computing Center of China, and the calculations were performed on a TianHe-2 systemthe characterizations supported by the Central Laboratory, School of Chemical and Material Engineering, Jiangnan University。
文摘Despite the intense research efforts directed to electrocatalytic nitrogen reduction reaction(eNRR),the NH_(3) yield and selectivity are still not up to the standard of practical application.Here,high-entropy perovskite oxides with composition Bax(FeCoNiZrY)_(0.2)O_(3−δ)(Bx(FCNZY)_(0.2)(x=0.9,1)are reported as eNRR catalysts.The eNRR activity of high-entropy perovskite oxide is enhanced by changing the nonstoichiometric metal elements at the A-site,thus generating additional oxygen vacancies.The NH_(3) yield and Faraday efficiency for B_(0.9)(FCNZY)_(0.2) are 1.51 and 1.95 times higher than those for B(FCNZY)_(0.2),respectively.The d-band center theory is used to theoretically predict the catalytically active center at the B-site,and as a result,nickel was identified as the catalytic site.The free energy values of the intermediate states in the optimal distal pathway show that the third protonation step(*NNH_(2)→*NNH_(3))is the rate-determining step and that the increase in oxygen vacancies in the high-entropy perovskite contributes to nitrogen adsorption and reduction.This work provides a framework for applying high-entropy structures with active site diversity for electrocatalytic nitrogen fixation.
基金supported by the National Natural Science Foundation of China (11434006, 11774199, and 51871112)the National Basic Research Program of China (2015CB921502)+1 种基金the 111 Project B13029supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DEAC02-76SF00515。
文摘Material functionalities strongly depend on the stoichiometry,crystal structure,and homogeneity.Here we demonstrate an approach of amorphous nonstoichiometric inhomogeneous oxides to realize tunable ferromagnetism and electrical transport at room temperature.In order to verify the origin of the ferromagnetism,we employed a series of structural,chemical,and electronic state characterizations.Combined with electron microscopy and transport measurements,synchrotron-based grazing incident wide angle X-ray scattering,soft X-ray absorption and circular dichroism clearly reveal that the roomtemperature ferromagnetism originates from the In0.23Co0.77O1-v,amorphous phase with a large tunable range of oxygen vacancies.The room-temperature ferromagnetism is tunable from a high saturation magnetization of 500 emu cm-3 to below 25 emu cm-3,with the evolving electrical resistivity from5×103μΩ cm to above 2.5×105 μΩ cm.Inhomogeneous nano-crystallization emerges with decreasing oxygen vacancies,driving the system towards non-ferromagnetism and insulating regime.Our work unfolds the novel functionalities of amorphous nonstoichiometric inhomogeneous oxides,which opens up new opportunities for developing spintronic materials with superior magnetic and transport properties.
