By simulating the electron paramagnetic resonance （EPR） and optical spectra on the basis of the 120 × 120 complete energy matrix, this paper determines the local lattice structure parameters R1 and R2 for MCl...By simulating the electron paramagnetic resonance （EPR） and optical spectra on the basis of the 120 × 120 complete energy matrix, this paper determines the local lattice structure parameters R1 and R2 for MCl：V2＋ （M=Na, K, Rb） systems at 77K, 195 K and RT （room temperature 295 K or 302 K）, respectively. The theoretical results indicate that there exists a compressed distortion in MCl：V2＋ systems. Meanwhile, it finds that the structure parameters R1, R2 and ｜△R｜（ = R1 - R2） increase with the rising temperature. Subsequently, from the analysis it concludes that the relation of EPR parameter D vs. △R is approximately linear. Finally, the effects of orbital reduction factor k on the g factors for the three systems have been discussed.展开更多
The local coordination structures around the doping Yb2＋ ions in sodium and potassium halides were calculated by using the first-principles supercell model. Both the cases with and without the charge compensation vac...The local coordination structures around the doping Yb2＋ ions in sodium and potassium halides were calculated by using the first-principles supercell model. Both the cases with and without the charge compensation vacancy in the local environment of the doping Yb2＋ were calculated to study the effect of the doping on the local coordination structures of Yb2＋. Using the calculated local structures, we obtained the crystal-field parameters for the Yb2＋ ions doped in sodium and potassium halides by a method based on the combination of the quantum-chemical calculations and the effective Hamiltonian method. The calculated crystal-field parameters were analyzed and compared with the fitted results.展开更多
The coordination structure of aluminum in magnesium aluminum hydroxide was studied by 27Al NMR. The result showed that tetrahedral aluminum (AlIV) existed in magnesium aluminum hydroxide, and the contents of AlIV inc...The coordination structure of aluminum in magnesium aluminum hydroxide was studied by 27Al NMR. The result showed that tetrahedral aluminum (AlIV) existed in magnesium aluminum hydroxide, and the contents of AlIV increased with the increase of the ratio of Al/Mg and with the peptizing temperature. AlIV originated from the so-called Al13 polymer with the structure of one Al tetrahedron surrounded by twelve Al octahedrons.展开更多
Improving the catalytic activity of non-noble metal single atom catalysts(SACs)has attracted considerable attention in materials science.Although optimizing the local electronic structure of single atom can greatly im...Improving the catalytic activity of non-noble metal single atom catalysts(SACs)has attracted considerable attention in materials science.Although optimizing the local electronic structure of single atom can greatly improve their catalytic activity,it often involves in-plane modulation and requires high temperatures.Herein,we report a novel strategy to manipulate the local electronic structure of SACs via the modulation of axial Co-S bond anchored onto graphitic carbon nitride(C_(3)N_(4))at room temperature(RT).Each Co atom is bonded to four N atoms and one S atom(Co-(N,S)/C_(3)N_(4)).Owing to the greater electronegativity of S in the Co-S bond,the local electronic structure of the Co atoms is available to be controlled at a relatively moderate level.Consequently,when employed for the photocatalytic hydrogen evolution reaction,the adsorption energy of intermediate hydrogen(H*)on the Co atoms is remarkably low.In the presence of the Co-(N,S)/C_(3)N_(4)SACs,the hydrogen evolution rates reach up to 10 mmol/(g·h),which is nearly 10 and 2.5 times greater than the rates in the presence of previously reported transition metal/C_(3)N_(4)and noble platinum nanoparticles(PtNPs)/C_(3)N_(4)catalysts,respectively.Attributed to the tailorable axial Co-S bond in the SAC,the local electronic structure of the Co atoms can be further optimized for other photocatalytic reactions.This axial coordination engineering strategy is universal in catalyst designing and can be used for a variety of photocatalytic applications.展开更多
The pursuit of high energy density while achieving long cycle life remains a challenge in developing transition metal(TM)oxide cathode materials for sodium-ion batteries(SIBs).Here,we present a concept of precisely ma...The pursuit of high energy density while achieving long cycle life remains a challenge in developing transition metal(TM)oxide cathode materials for sodium-ion batteries(SIBs).Here,we present a concept of precisely manipulating structural evolution via local coordination chemistry regulation to design high-performance composite cathode materials.The controllable structural evolution process is realized by tuning magnesium content in Na0.6Mn1-xMgxO2,which is elucidated by a combination of experimental analysis and theoretical calculations.The substitution of Mg into Mn sites not only induces a unique structural evolu-tion from layered–tunnel structure to layered structure but also mitigates the Jahn–Teller distortion of Mn3+.Meanwhile,benefiting from the strong ionic inter-action between Mg2+and O2-,local environments around O2-coordinated with electrochemically inactive Mg2+are anchored in the TM layer,providing a pinning effect to stabilize crystal structure and smooth electrochemical profile.The layered–tunnel Na0.6Mn0.95Mg0.05O2 cathode material delivers 188.9 mAh g-1 of specific capacity,equivalent to 508.0 Wh kg-1 of energy density at 0.5C,and exhibits 71.3%of capacity retention after 1000 cycles at 5C as well as excellent compatibility with hard carbon anode.This work may provide new insights of manipulating structural evolution in composite cathode materials via local coordi-nation chemistry regulation and inspire more novel design of high-performance SIB cathode materials.展开更多
As one important member of main group metals,magnesium(Mg)takes great parts in fields involving biology,medicine,industry,and some others.Because of the unique characteristics including but not limited to low-cost,non...As one important member of main group metals,magnesium(Mg)takes great parts in fields involving biology,medicine,industry,and some others.Because of the unique characteristics including but not limited to low-cost,non-toxic and light-weight,Mg-based coordination polymers(CPs)with good performances such as gas storage and separation,catalysis and fluorescence have received certain attention in recent years.However,compared with the well-studied transition metal and rare earth metal based CPs,the report on Mg-CPs is relatively scarce.In this review we briefly summarize the synthesis,structural features,and fluorescent(FL)properties of Mg-CPs on the basis of recent related advances made in our lab.The chemical sensing,white emitting,and mechanoresponsive photoluminescence of selected FL-Mg-CPs are emphasized.展开更多
基金Project supported by the National Natural Science Foundation of China (Grant No 10774103)the Doctoral Education Fund of the Education Ministry of China (Grant No 20050610011)
文摘By simulating the electron paramagnetic resonance （EPR） and optical spectra on the basis of the 120 × 120 complete energy matrix, this paper determines the local lattice structure parameters R1 and R2 for MCl：V2＋ （M=Na, K, Rb） systems at 77K, 195 K and RT （room temperature 295 K or 302 K）, respectively. The theoretical results indicate that there exists a compressed distortion in MCl：V2＋ systems. Meanwhile, it finds that the structure parameters R1, R2 and ｜△R｜（ = R1 - R2） increase with the rising temperature. Subsequently, from the analysis it concludes that the relation of EPR parameter D vs. △R is approximately linear. Finally, the effects of orbital reduction factor k on the g factors for the three systems have been discussed.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 11074315, 11074245, 90922022, and 11111120060)the Russian Foundation for Basic Research (Grant No. 11-02-91152)the European Social Fund (Grant No. MTT50)
文摘The local coordination structures around the doping Yb2＋ ions in sodium and potassium halides were calculated by using the first-principles supercell model. Both the cases with and without the charge compensation vacancy in the local environment of the doping Yb2＋ were calculated to study the effect of the doping on the local coordination structures of Yb2＋. Using the calculated local structures, we obtained the crystal-field parameters for the Yb2＋ ions doped in sodium and potassium halides by a method based on the combination of the quantum-chemical calculations and the effective Hamiltonian method. The calculated crystal-field parameters were analyzed and compared with the fitted results.
基金This research is supported by NNSFC No:20273041.
文摘The coordination structure of aluminum in magnesium aluminum hydroxide was studied by 27Al NMR. The result showed that tetrahedral aluminum (AlIV) existed in magnesium aluminum hydroxide, and the contents of AlIV increased with the increase of the ratio of Al/Mg and with the peptizing temperature. AlIV originated from the so-called Al13 polymer with the structure of one Al tetrahedron surrounded by twelve Al octahedrons.
基金National Natural Science Foundation of China(No.22008251)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515010318)Shenzhen Science and Technology Program(No.JCYJ20220531095813031).
文摘Improving the catalytic activity of non-noble metal single atom catalysts(SACs)has attracted considerable attention in materials science.Although optimizing the local electronic structure of single atom can greatly improve their catalytic activity,it often involves in-plane modulation and requires high temperatures.Herein,we report a novel strategy to manipulate the local electronic structure of SACs via the modulation of axial Co-S bond anchored onto graphitic carbon nitride(C_(3)N_(4))at room temperature(RT).Each Co atom is bonded to four N atoms and one S atom(Co-(N,S)/C_(3)N_(4)).Owing to the greater electronegativity of S in the Co-S bond,the local electronic structure of the Co atoms is available to be controlled at a relatively moderate level.Consequently,when employed for the photocatalytic hydrogen evolution reaction,the adsorption energy of intermediate hydrogen(H*)on the Co atoms is remarkably low.In the presence of the Co-(N,S)/C_(3)N_(4)SACs,the hydrogen evolution rates reach up to 10 mmol/(g·h),which is nearly 10 and 2.5 times greater than the rates in the presence of previously reported transition metal/C_(3)N_(4)and noble platinum nanoparticles(PtNPs)/C_(3)N_(4)catalysts,respectively.Attributed to the tailorable axial Co-S bond in the SAC,the local electronic structure of the Co atoms can be further optimized for other photocatalytic reactions.This axial coordination engineering strategy is universal in catalyst designing and can be used for a variety of photocatalytic applications.
基金National Natural Science Foundation of China,Grant/Award Numbers:51772093,51971124,52171217,52202284National Key Research and Devel opment Programs,Grant/Award Number:2021YFB2400400+4 种基金Zhejiang Natural Science Foundation,Grant/Award Number:LQ23E020002WenZhou Natural Science Foundation,Grant/Award Numbers:G20220019,G20220021State Key Laboratory of Electrical Insulation and Power Equipment,Xi'an Jiaotong University,Grant/Award Number.EIPE22208Cooperation between Industry and Education Project of Ministry of Education,Grant/Award Number:220601318235513Doctoral Innovation Foundation of Wenzhou University,Grant/Award Number.3162023001001。
文摘The pursuit of high energy density while achieving long cycle life remains a challenge in developing transition metal(TM)oxide cathode materials for sodium-ion batteries(SIBs).Here,we present a concept of precisely manipulating structural evolution via local coordination chemistry regulation to design high-performance composite cathode materials.The controllable structural evolution process is realized by tuning magnesium content in Na0.6Mn1-xMgxO2,which is elucidated by a combination of experimental analysis and theoretical calculations.The substitution of Mg into Mn sites not only induces a unique structural evolu-tion from layered–tunnel structure to layered structure but also mitigates the Jahn–Teller distortion of Mn3+.Meanwhile,benefiting from the strong ionic inter-action between Mg2+and O2-,local environments around O2-coordinated with electrochemically inactive Mg2+are anchored in the TM layer,providing a pinning effect to stabilize crystal structure and smooth electrochemical profile.The layered–tunnel Na0.6Mn0.95Mg0.05O2 cathode material delivers 188.9 mAh g-1 of specific capacity,equivalent to 508.0 Wh kg-1 of energy density at 0.5C,and exhibits 71.3%of capacity retention after 1000 cycles at 5C as well as excellent compatibility with hard carbon anode.This work may provide new insights of manipulating structural evolution in composite cathode materials via local coordi-nation chemistry regulation and inspire more novel design of high-performance SIB cathode materials.
基金funded by the NSF of Fujian Province(2018J05033)。
文摘As one important member of main group metals,magnesium(Mg)takes great parts in fields involving biology,medicine,industry,and some others.Because of the unique characteristics including but not limited to low-cost,non-toxic and light-weight,Mg-based coordination polymers(CPs)with good performances such as gas storage and separation,catalysis and fluorescence have received certain attention in recent years.However,compared with the well-studied transition metal and rare earth metal based CPs,the report on Mg-CPs is relatively scarce.In this review we briefly summarize the synthesis,structural features,and fluorescent(FL)properties of Mg-CPs on the basis of recent related advances made in our lab.The chemical sensing,white emitting,and mechanoresponsive photoluminescence of selected FL-Mg-CPs are emphasized.
基金supported by the National Natural Science Foundation of China(21373251)Main Direction Program of Knowledge Innovation of Chinese Academy of Sciences,China(KZCX2-EW-307)~~
