Nature Communications
·
2024
·Vol. 15
·期 1
·1-11
·
IF 14.7
Huang Jiangfeng,Xue Liang,Huang Yin,Jiang Yanchen,Wu Ping,Fan Xiulin,Zhu Junwu
LiMn 2 O 4 (LMO) is an attractive positive electrode material for aqueous lithium-ion batteries (ALIBs), but its inferior cycle performance limits the practical application. The degradation mechanism of LMO in ALIBs is still unclear, resulting in inability to predictably improve its structural stability. The electrode/electrolyte interface is believed to play an important role in electrode degradation. However, the interactions of the water-containing electrode/electrolyte interface of LMO are underexplored. In this work, we demonstrate the insertion of H 3 O + into LMO during cycling in aqueous electrolyte and elucidate the paradoxical effects of H 3 O + . The crystal H 3 O + enhances the structural stability of LMO by forming a gradient Mn 4+ -rich protective shell, but an excess amount of crystal H 3 O + leads to poor Li + conductivity, resulting in rapid capacity fading. Combining electrochemical analyses, structural characterizations, and first-principles calculations, we reveal the intercalation of H 3 O + into LMO and its associated mechanism on the structural evolution of LMO. Furthermore, we regulate the crystal H 3 O + content in LMO by modifying the hydrogen bond networks of aqueous electrolyte to restrict H 2 O molecule activity. This approach utilizes an appropriate amount of crystal H 3 O + to enhance the structural stability of LMO while maintaining sufficient Li + diffusion.
研究领域:
材料科学
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电化学
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PubMed
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
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2019
·
IF 4.561
Chunlan Li,Wensheng Liu,Yunzhu Ma
In-depth insight into the structure of oligomers in sols plays an important role in determining the structure and properties of the final materials, such as aluminium borosilicate fibers, flakes, microspheres and composites. In this study, the influence of H 3 O + on the structure formation of oligomers in sols prepared from basic aluminium acetate (BAA) was studied by Fourier-transform infrared spectroscopy (FT-IR), 27 Al NMR spectroscopy and density functional theory (DFT) calculation. The results indicated that BAA consisting of tetrahedral Al species existed in dimeric form (BAA2-2). The polymerization of BAA2-2 was more thermodynamically favourable than its hydrolysis both in neutral and acidic solutions. The oligomers formed in neutral aqueous solution were beneficial to prepare different polymers with dendritic or three-dimensional structures. The oligomers formed in acidic solution (H + /BAA = 0.5) were mostly linear tetramers composed of three octahedral and one tetrahedral Al species, which were beneficial to the spinnability of sols during the preparation of ceramic fibers. The addition of H + changed the electronic properties of Al(III) and significantly promoted the coordination ability of water and Al 3+ , leading to an increase in the octahedral Al species and a great change in the structure of the sol. The DFT results were consistent with the experimental results, which provided a necessary theoretical guidance to improve the properties of aluminium sols and meet the needs of the final materials.
研究领域:
材料科学
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化学
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高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
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2023
·
IF 3.3
Yue-Ling Sun,Gang-Xiang Liu,Yi-Lei Lv,Liang Ma,Wen-Dong Yao,Ru-Ling Tang
Phosphate crystals are valuable materials according to their diverse structures and physical and chemistry properties. A zinc orthophosphate, (NH 4 ) 3 (H 3 O)Zn 4 (PO 4 ) 4 , has been obtained via hydrothermal route. It was crystallized in hexagonal space group P 6 3 , featuring a three-dimensional (3D) [Zn(PO 4 )] – anion network built by corner-sharing connected ZnO 4 and PO 4 tetrahedra. The NH 4 + and H 3 O + units are located in the six-member cavities of the framework as the balanced cations. (NH 4 ) 3 (H 3 O)Zn 4 (PO 4 ) 4 exhibits a moderate and phase matchable second harmonic generation effect (SHG) about 1.4 times of KH 2 PO 4 (KDP), which is the strongest in zinc orthophosphates. Besides structural features, optical properties measurements and theoretical analyses of (NH 4 ) 3 (H 3 O)Zn 4 (PO 4 ) 4 were performed.
研究领域:
材料科学
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光学
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晶体学
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化学
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DOI
高影响因子
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
·
2016
·Vol. 642
·期 4
·343-349
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IF 1.261
Xiao Zhao,Dajiang Mei,Jingli Xu,Yuandong Wu
Three compounds A Sb 2 (SO 4 ) 2 (PO 4 ) ( A = H 3 O + , K, Rb) were obtained from the reactions of Sb 2 O 3 , A 2 CO 3 ( A = Li, Rb) or K 2 SO 4 and NH 4 H 2 PO 4 in H 2 SO 4 (98 %) at 220–250 °C. Their structures were determined by single-crystal X-ray diffraction. All compounds crystallize in the triclinic space group P (no.2) and are isostructural. The crystal structures consist of two-dimensional 2 ∞ [Sb 2 (SO 4 ) 2 (PO 4 )] – anionic layers and alkali cations, which are located between anionic layers. The anionic layers are composed of [SbO 4 ] ψ-trigonal bipyramids, [SbO 5 ] ψ octahedra, [SO 4 ] tetrahedra, and [PO 4 ] tetrahedra. All compounds are characterized by solid state UV/Vis/NIR diffuse reflectance spectra, FT-IR spectroscopy, and Raman spectroscopy.
研究领域:
化学
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材料科学
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高影响因子
INORGANIC CHEMISTRY
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2016
·
IF 4.82
Bing-Ping Yang,Chun-Li Hu,Xiang Xu,Jiang-Gao Mao
A new series of platinum iodates, namely, α-(H3O)2Pt(IO3)6, β-(H3O)2Pt(IO3)6, and A2Pt(IO3)6 (A = Na, K, Rb, Cs), have been synthesized. Interestingly, among these six stoichiometrically identical compounds, α-(H3O)2Pt(IO3)6 is polar, whereas other compounds are nonpolar and centrosymmetric. They all consist of zero-dimensional [Pt(IO3)6]2– molecular units separated by H3O+ or A+ cations. All of the lone electron pairs of the IO3– groups are aligned and almost point to one direction for α-(H3O)2Pt(IO3)6, whereas IO3– groups are located trans to each other in other compounds. The material, α-(H3O)2Pt(IO3)6, exhibits very strong second harmonic generation (SHG) effects, approximately 1.2 × KTiOPO4 (KTP), and is phase-matchable. Thermogravimetric analysis, elemental analysis, infrared spectra, UV–vis spectra, nonlinear optical properties, and theoretical calculations are also reported.
研究领域:
材料科学
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化学
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光学
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DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2021
·
IF 19.503
Shenghua Ye,Yaqi Lei,Tingting Xu,Lirong Zheng,Zhida Chen,Xiuyuan Yang,Xiangzhong Ren,Yongliang Li,Qianling Zhang,Jianhong Liu
In this study, phosphate FeCo(H 3 O)(PO 4 ) 2 nanosheet arrays (NAs) were synthesized using an electrochemical strategy. FeCo(H 3 O)(PO 4 ) 2 NAs as precatalyst could undergo significant self-reconstruction, including leaching of phosphate anions and electro-oxidation of Co 2+ during anodizing at the potential range of oxygen evolution reaction (OER) in 1 M KOH solution, eventually resulting in the formation of Fe 0.5 Co 0.5 OOH NAs with low crystallinity . The high content of Fe in Fe 0.5 Co 0.5 OOH NAs promoted the formation of active Fe 3+ –O–Fe 3+ motifs that increased OER occurrence. Additionally, Fe incorporation increased the ratio of the reaction rate constants of oxygen evolution to Co 3+ /Co 4+ (k OER /k M,ox ) and enhanced the reaction order on the hydroxyl ion . These factors significantly contributed to the outstanding OER catalytic performances of Fe 0.5 Co 0.5 OOH NAs.
研究领域:
材料科学
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电化学
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高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
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2017
·
IF 2.299
Tong-Ying Chang,Chun-Li Hu,Dong Yan,Jiang-Gao Mao
Two new phosphates, non-centrosymmetric (NCS) (H 3 O)Ca 2 Zn 3.5 (PO 4 ) 4 and centrosymmetric (CS) Ba 2 Cd 3 (PO 4 ) 2 (HPO 4 ) 2 have been prepared by hydrothermal reactions . The single-crystal X-ray structural analyses have shown that they crystallized in space group P −42 1 c and P2 1 /c , respectively·(H 3 O)Ca 2 Zn 3.5 (PO 4 ) 4 features a three-dimensional (3D) network structure composed of ZnO 4 and PO 4 tetrahedra that are interconnected via corner-sharing, forming 1D channels of 6-MRs and 8-MRs which are filled by Ca 2+ and H 3 O + cations, respectively. Ba 2 Cd 3 (PO 4 ) 2 (HPO 4 ) 2 features a layered [Cd 3 (PO 4 ) 2 (HPO 4 ) 2 ] 4- composed of 1D chain of edge-sharing CdO 6 octahedra that are further bridged by PO 4 tetrahedra with Ba 2+ cations filling the interlayer spaces. Luminescent studies suggest that (H 3 O)Ca 2 Zn 3.5 (PO 4 ) 4 emits blue light. Optical diffuse reflectance spectra show the experimental band gaps for (H 3 O)Ca 2 Zn 3.5 (PO 4 ) 4 and Ba 2 Cd 3 (PO 4 ) 2 (HPO 4 ) 2 are 5.67 eV and 5.68 eV, respectively. The UV cut-off edge of title compounds are around at 218 nm·(H 3 O)Ca 2 Zn 3.5 (PO 4 ) 4 exhibits a very weak SHG response.
研究领域:
材料科学
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晶体学
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高影响因子
INORGANIC CHEMISTRY
·
2021
·
IF 5.165
Yuan-Bin Fang,Rui-Biao Fu,Hong-Xin Tang,Qi-Rui Shui,Zu-Ju Ma,Xin-Tao Wu
Nonlinear-optical (NLO) crystal is an important photoelectric functional material. In this work, a new NLO titanium iodate, (H3O)2Ti(IO3)6, along with Ti(IO3)4 has been synthesized under facile conditions. The space group of (H3O)2Ti(IO3)6 is the chiral noncentrosymmetric group R3 (No. 146), with an interesting three-dimensional framework, while that of Ti(IO3)4 is the centrosymmetric space group P1̅ (No. 2) containing one-dimensional chains. Thermogravimetric analysis shows that (H3O)2Ti(IO3)6 and Ti(IO3)4 have no weight loss below 220 and 390 °C, respectively. In addition, (H3O)2Ti(IO3)6 not only is thermally stable up to 200 °C in an air atmosphere but also is stable in water. (H3O)2Ti(IO3)6 has a moderate-intensity second-harmonic-generation (SHG) response (1.4×KDP), a large laser-induced damage threshold (46×AgGaS2), and high transmittance in the wavelength ranges of 0.5–1.4 and 2.5–10 μm. Both local dipole moment and systematic theoretical calculations reveal that the SHG response of (H3O)2Ti(IO3)6 is mainly because of the combined effect of [TiO6] octahedra and IO3 and IO4 units. In a word, (H3O)2Ti(IO3)6 exhibits good NLO performances, as well as water resistance and facile growth of a single crystal with high quality, indicating its potential application as NLO materials in the visible and mid-IR regions, especially the visible region.
研究领域:
材料科学
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光学
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晶体学
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PubMed
高影响因子
INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Qian Wu,Tianyu Wang,Jingfang Zhou,Pifu Gong,Haochen Li,Haotian Tian,Mingjun Xia
With the increasing significance of the laser industry, especially in the 3–5 μm range, mid-infrared (mid-IR) nonlinear optical (NLO) crystals have become crucial components to meet stringent requirements. Herein, a large birefringence is essential for a mid-IR NLO crystal, as it ensures the phase-matching condition for high-conversion efficiency in laser output operation. In this study, three vanadium selenites A(VO2)3(SeO3)2 (A = NH4+, K+, and H3O+) with hexagonal tungsten oxide-related structures were prepared, featuring two-dimensional layered structures composed of two second-order Jahn–Teller (SOJT) motifs: distorted VO6 octahedra and SeO3 pyramids. Owing to the highly anisotropic VO6 octahedra and SeO3 pyramids, the family of A(VO2)3(SeO3)2 (A = NH4+, K+, and H3O+) crystals shows significant birefringence, which represents the highest birefringence value among vanadium selenites, even surpassing some SOJT-cation-based oxides. In addition, the title crystals exhibit large second harmonic generation responses of powder of 0.28–0.58 × AgGaS2 (AGS) at 2.09 μm.
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高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Haitao Zhou,Zhizhuo Yang,Xueqin Wu,Kun Huang
The separation process in hydrochloric acid environments is determined by the interfacial chemistry of the acid. However, the surface species of concentrated acids are complex. The effect of dominant species on the surface of concentrated acids and their dissociation behavior on interfacial separation has been the focus of academic debate. The extraction and separation of two typical anions, PdCl 4 2− and PtCl 6 2− , with different hydration characters on the surface of concentrated hydrochloric acid were investigated by thin layer extraction (TLX). A new phenomenon was discovered that the effect of hydrochloric acid concentration, extractant concentration, organic film thickness, and shear flow rate on the extraction of easily hydrated PdCl 4 2− anions is greater than that of hardly hydrated PtCl 6 2− . However, during the conventional SX process, the phenomenon cannot be observed due to the continuous dispersion and aggregation of oil droplets. It found that HCl molecules only dissociate into solvated H 3 O +… Cl − ion pairs on the surface of concentrated hydrochloric acid, but not H 3 O + and Cl − ions respectively. The concentration of dissociated H 3 O + ions at the interface is lower than that in the bulk phase. The protonation of the A336 molecule promotes the migration of dissociated H 3 O + ions in the bulk phase towards the interface. Because the PdCl 4 2− anions are more likely to be hydrated than PtCl 6 2− anions and combine with H 3 O + ions, the orderly migration of H 3 O + ions in the laminar boundary layer towards the interface drives the mass transfer of easily hydrated PdCl 4 2− anions. The anion exchange between PdCl 4 2− and Cl − ions associated with the A336 molecules results in a higher concentration of Cl − ions enriched at the interface than that in the bulk phase. The migration of easily hydrated Cl − ions towards the bulk phase would drag the water molecules around PtCl 6 2− anions and therefore inhibit the mass transfer of PtCl 6 2− anions. The orderly reverse migration of H 3 O + and Cl − ions enhances the separation between easily hydrated PtCl 6 2− and hardly hydrated PdCl 4 2− anions. This study offers a new perspective on the dissociation of species on the surface of concentrated hydrochloric acid and its impact on separation processes.
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高影响因子
CRYSTENGCOMM
·
2021
·Vol. 23
·期 19
·3549-3556
·
IF 3.545
Yuan Lin,Huijie Jiang,Guangling Liang,Wei-Hua Deng,Qiaohong Li,Wen-Hua Li,Gang Xu
A new conductive coordination polymer (CCP), Ag(SPh–NO2)·AgNO3, with a three-dimensional (3D) non-porous structure composed of a unique 2D inorganic layered structure linked by an organic linker, was reported. The 3D CCP Ag(SPh–NO2)·AgNO3 exhibits semiconductor behavior, with electronic conductivity as high as 2.7 × 10−6 S cm−1 at 295 K, which is comparable to the vast majority of highly conductive 3D coordination polymers. The chemiresistive humidity sensing ability of Ag(SPh–NO2)·AgNO3 was studied over a wide relative humidity (RH) range (10–90% RH) at room temperature. The sensor showed exceptionally high moisture responsiveness, with a 106-fold increase in response at 90% RH and excellent sensitivity to humidity in the range of 10–80% RH. The sensing mechanism was further studied using alternating current (AC) impedance spectroscopy and direct current (DC) instantaneous reverse polarity experiments. The exceptionally high response of the Ag(SPh–NO2)·AgNO3-based sensor at high RH is attributed to the periodic arrangement of the ion species via reversible coordination bonds in the structure. H3O+ and Ag+ are easily formed on its hydrophilic surface, through which the free transport of ionic carriers dominates the conductivity change. Using density functional theory (DFT) calculations, it is further demonstrated that the reversibly coordinated AgNO3 in the structure can be easily occupied by water molecules, which is thermodynamically spontaneous in the presence of humidity. Furthermore, the functional AgNO3 groups and their reversible coordination bonds enabled Ag(SPh–NO2)·AgNO3 to show exceptionally high moisture responsiveness.
研究领域:
材料科学
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化学
·
传感器
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电化学
·
计算化学
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高影响因子
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