Synchrotron Radiation-based X-ray Research Articles

Enhancement of arsenopyrite bioleaching by different Fe(III) compounds through changing composition and structure of passivation layer

Ferric iron has a significant effect on the bioleaching of arsenopyrite, the most efficient way for pretreatment of arsenopyrite-bearing gold ores. Up to date, the differential effect of Fe(III) compounds on that process was rarely studied. Herein, FeCl3, Fe(NO3)3 and Fe2O3 were addressed to unravel their different promotion effects during arsenopyrite biooxidation by Sulfobacillus thermosulfidooxidans, in which the As/Fe/S speciation transformation were comprehensively analyzed mainly with synchrotron radiation-based X-ray diffraction (SR-XRD) and Fe L- and As/S K-edge X-ray absorption near edge structure (XANES) spectroscopy to detect the elimination of passivation, besides the changes in the morphology and the leaching parameters of the mineral. The results showed that, the bioleaching of arsenopyrite was efficiently promoted under addition of the Fe(III) compounds (0.6 g/L), for instance, the extraction rates of As were increased from 55% to 64–77%, the surface of arsenopyrite suffered more serious corrosion and covered with a loose and porous structure, the intermediates S0, thiosulfate and orpiment significantly decreased, and jarosites and schwertmannite increased, the remaining content of arsenopyrite was decreased from 31.5% to 21.7–5.3%. Those results indicated that, the iron/sulfur oxidation activity was enhanced and the transformation of those intermediates was accelerated by the Fe(III) compounds added. Such change intension accompanied with the promotion effect observes the order FeCl3 > Fe(NO3)3 > Fe2O3. These results reveale that the adding Fe(III) compounds, especially for FeCl3, can efficiently promote the biooxidation through removal of some intermediates from the surface of the arsenopyrite and thus optimize the pretreatment of arsenopyrite-bearing gold ores.

Trabecular architecture during the healing process of a tibial diaphysis defect

The adaptation of trabecular bone microstructure to mechanical loads has been intensively investigated. However, loading-unrelated aspects of trabecular architecture remain unclear. We used synchrotron radiation-based X-ray microtomography to study the 3D microarchitecture of newly formed trabecular tissue in a defect produced in the cortical region of the rat tibia diaphysis, in the absence (7, 14, and 21 days) or the presence (21 days) of carbonated hydroxyapatite/alginate (cHA) microspheres. This work provides the first evidence that the woven bone trabecular network, formed during the healing process, displays a well-organized 3D microarchitecture consisting of nodes with 3 (3-N), 4 (4-N) and 5 (5-N) connecting trabeculae, with a mean relative abundance of (3-N)/(4-N)/(5-N) = 66/24/7, for the analyzed periods. The measured inter-trabecular angles (ITA) distribution presented a Gaussian profile, with mean value at 115° for 3-N nodes, and 105° for 4-N nodes, close to the angles of idealized 3D regular structures (120° and 109.5°, respectively). Changes in the dispersion of ITA distribution suggested that a highly symmetric trabecular fabric organized under tensegrity principles is formed early during the bone healing process. Post-implantation, cHA disaggregated into multiple fragments (~20–400 μm), stimulating osteoconduction and bone growth toward the interior of the medullary cavity. The presence of biomaterials in bone defects affected the trabecular dimensions; however, it did not interfere with the formation of geometrical motifs with topological parameters similar to those found in the sham-defects. Statement of SignificanceThe trabecular bone microstructure enables the tissue to meet the necessary mechanical and functional demands. However, the process of trabecular microarchitecture formation during healing, in the absence or presence of a bone graft, is not yet well understood. This work demonstrated that, from the beginning of its formation in cortical bone defects, the woven-bone trabecular network is spatially organized according to the principle of tensegrity. This microarchitecture is comprised of highly symmetric geometric motifs and is an intrinsic characteristic of trabecular growth, regardless of hierarchical scale or mechanical stimulation. The addition of a biodegradable nanostructured calcium phosphate graft did not disrupt trabecular microarchitecture; however, graft biodegradation should be controlled to optimize the reproduction of intrinsic trabecular motifs throughout the defect.

Shedding Light on Metal-Based Nanoparticles in Zebrafish by Computed Tomography with Micrometer Resolution.

Metal-based nanoparticles are clinically used for diagnostic and therapeutic applications. After parenteral administration, they will distribute throughout different organs. Quantification of their distribution within tissues in the 3D space, however, remains a challenge owing to the small particle diameter. In this study, synchrotron radiation-based hard X-ray tomography (SRμCT) in absorption and phase contrast modes is evaluated for the localization of superparamagnetic iron oxide nanoparticles (SPIONs) in soft tissues based on their electron density and X-ray attenuation. Biodistribution of SPIONs is studied using zebrafish embryos as a vertebrate screening model. This label-free approach gives rise to an isotropic, 3D, direct space visualization of the entire 2.5 mm-long animal with a spatial resolution of around 2 µm. High resolution image stacks are available on a dedicated internet page (http://zebrafish.pharma-te.ch). X-ray tomography is combined with physico-chemical characterization and cellular uptake studies to confirm the safety and effectiveness of protective SPION coatings. It is demonstrated that SRμCT provides unprecedented insights into the zebrafish embryo anatomy and tissue distribution of label-free metal oxide nanoparticles.

Advances in Synchrotron Radiation-based X-ray Absorption Spectroscopy to Characterize the Fine Atomic Structure of Single-atom Nanozymes.

Single-atom nanozymes (SAzymes) with high atomic utilization, excellent catalytic activities, and selectivity have recently attracted significant interest. Usually, they contain only isolated metal atoms embedded in host matrices. However, traditional measuring instruments are extremely difficult to obtain their useful structural information due to ultra-low metal loading, amorphous structure, coordination with light-weight surface atoms and/or co-existing of other metal elements. Synchrotron radiation-based X-ray absorption fine structure spectroscopy (XAFS) has demonstrated its usefulness for this type of catalyst. In this mini-review, we have summarized the recent progress using XAFS to characterize the fine atomic structure of these nanozymes. The synthetic strategies of SAzymes, the principle of XAFS, delicate structural information by XAFS, and the applications of SAzymes have been presented. Furthermore, the outlook and challenges in this active research field have also been discussed. We expect that the help of XAFS can offer a wealth of opportunities to design and develop more efficient SAzymes and apply them to various fields.

Single atoms or not? The limitation of EXAFS

Single atom catalysts (SACs) have recently attracted much attention. To identify the single atom materials, a combination of high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and synchrotron radiation-based extended x-ray absorption fine structure (EXAFS) is typically used. However, the present work reveals that EXAFS is not sensitive enough to identify single atoms in many cases, which may easily confuse the contributions from small clusters or nanoparticles due to the polydispersity and disorder effects. Also, HAADF-STEM measures very limited regions, which may easily miss other compositions. The real catalytic sites in various reactions could be significantly different from the single atom sites due to the complicated compositions in the so-called “SACs,” which may also lead to misunderstanding of the working mechanism.

Effect of Long-term Administration of Prostaglandin E1 on Morphologic Changes in Ductus Arteriosus

To improve survival of patients with hypoplastic left heart syndrome, combination therapy with bilateral pulmonary artery banding and prostaglandin E1 (PGE1)-mediated ductal patency was developed as an alternative for high-risk neonates in Japan. However, the effect of long-term PGE1 administration on ductus arteriosus remains unclear. Synchrotron radiation-based X-ray phase-contrast tomography (XPCT) enables clear visualization of soft tissues at an approximate spatial resolution of 12.5 μm. We aimed to investigate morphologic changes in ductus arteriosus after long-term PGE1 infusion using XPCT. Seventeen ductus arteriosus tissue samples from patients with hypoplastic left heart syndrome were obtained during the Norwood procedure. The median duration of lipo-prostaglandin E1 (lipo-PGE1) administration was 48 days (range, 3 to 123). Structural analysis of ductus arteriosus was performed and compared with conventional histologic analysis. The XPCT was successfully applied to quantitative measurements of ductal media. Significant correlation was found between the duration of lipo-PGE1 infusion and mass density of ductal media (R= 0.723, P= .001). The duration of lipo-PGE1 administration was positively correlated with elastic fiber staining (R= 0.799, P < .001) and negatively correlated with smooth muscle formation (R=-0.83, P < .001). No significant increase in intimal cushion formation was found after long-term lipo-PGE1 administration. Expression of ductus arteriosus dominant PGE2-receptor EP4 almost disappeared in specimens when lipo-PGE1 was administered over 3 days. Disorganized elastogenesis and little intimal cushion formation after long-term lipo-PGE1 administration suggest that ductus arteriosus remodeled to the elastic artery phenotype. Because EP4 was downregulated and ductus arteriosus exhibited elastic characteristics, the dosage of lipo-PGE1 might be decreased after a definite administration period.

Testing the activation temperature of non-evaporable Ti-Zr-Hf-V getter films by XPS

Developing new non-evaporable getter (NEG) films with low activation temperature is the key to developing next generation high-energy particle accelerators with the ultimate degree of chamber vacuum. Here, a quaternary alloy Ti-Zr-Hf-V getter film with a uniform thickness of 1.64μm is fabricated by DC magnetron sputtering. The activation temperature of the Ti-Zr-Hf-V getter film was detected by measuring the binding energy of Ti, Zr, Hf and V at different temperatures through in situ synchrotron radiation-based X-ray photoelectron spectroscopy. The Ti-Zr-Hf-V getter films are found to be activated at a temperature of 150 ∘C. In addition, the binding energy of Hf 4f at 130 ∘C is basically the same as that at 300 ∘C. The presence of the Hf element reduces the activation temperature of the obtained films.

Synthesis of Monolayer Blue Phosphorus Enabled by Silicon Intercalation.

The growth of entirely synthetic two-dimensional (2D) materials could further expand the library of naturally occurring layered solids and provide opportunities to design materials with finely tunable properties. Among them, the synthesis of elemental 2D materials is of particular interest as they represent the chemically simplest case and serve as a model system for exploring the on-surface synthesis mechanism. Here, a pure atomically thin blue phosphorus (BlueP) monolayer is synthesized via silicon intercalation of the BlueP-Au alloy on Au(111). The intercalation process is characterized at the atomic scale by low-temperature scanning probe microscopy and further corroborated by synchrotron radiation-based X-ray photoelectron spectroscopy measurements. The evolution of the band structures from the BlueP-Au alloy into Si-intercalated BlueP are clearly revealed by angle-resolved photoemission spectroscopy and further verified by density functional theory calculations.

Jawbone remodeling: a conceptual study based on Synchrotron High-resolution Tomography

One of the most important aspects of bone remodeling is the constant turnover mainly driven by the mechanical loading stimulus. The remodeling process produces changes not only in the bone microarchitecture but also in the density distribution of the mineralized matrix - i.e. in calcium concentrations- and in the osteocyte lacunar network. Synchrotron radiation-based X-ray microtomography (microCT) has proven to be an efficient technique, capable to achieve the analysis of 3D bone architecture and of local mineralization at different hierarchical length scales, including the imaging of the lacuno-canalicular network. In the present study, we used microCT within a conceptual study of jawbone remodeling, demonstratively focusing the investigation in two critical contexts, namely in the peri-dental and the peri-implant tissues. The microCT analysis showed that a relevant inhomogeneity was clearly present in both peri-dental and peri-implant biopsies, not only in terms of microarchitecture and mineralization degree, but also considering the lacunar network, i.e. size and numerical density of the osteocyte lacunae. The correlated histological results obtained on the same samples confirmed these observations, also adding information related to non-mineralized tissues. Despite its demonstrative nature, it was concluded that the proposed method was powerful in studying jawbone remodeling because it revealed a direct correlation of its rate with the lacunar density, as achieved by the analysis of the osteocyte lacunar network, and an inverse correlation with the local bone mineral density, as revealed with the Roschger approach.

Insight Into the Crystallinity of Chinese Ancient Silk by Synchrotron Radiation-Based and Conventional X-ray Diffraction Methods

This study investigates the crystallinity distribution of ancient silk. Owing to the inherent multi-hierarchical structure of silk protein and the complicated structural changes that occur due to various burial environments, it is challenging but worthwhile to study ancient silk ageing behavior, which is based on the fact that ageing begins with a single fiber and then spreads to a whole fabric. Crystallinity was one of the most effective indicators found to reveal the ageing status of silk. Therefore, a synchrotron radiation-based X-ray diffraction(SR-XRD) method was employed to study the crystallinity distribution of single fibers of ancient silk unearthed from seven archaeological sites in China from historical periods including the warring states, Han dynasty, Song dynasty, and Ming dynasty. In comparison, the conventional X-ray diffraction method, which uses large amounts of samples, was also performed to determine the integral crystallinity of ancient silk. Thermal stability experiments by thermogravimetry(TG) as well as morphology observations by scanning electron microscopy(SEM) and optical microscopy(OM) all confirmed the deterioration of ancient silk. Moreover, the ageing mechanism of ancient silk was proposed with the assistance of an artificial ageing study. The results confirmed the effectiveness of SR-XRD as an ageing indicator, revealing the crystallinity distribution. This research could provide motivation to determine the deterioration status of ancient silk, and would also aid in explaining the fragility of ancient silk due to ageing.

Understanding Photoelectrochemical Water Oxidation with X-ray Absorption Spectroscopy

Synchrotron radiation-based X-ray absorption spectroscopy (XAS) has been demonstrated to be a powerful and effective characterization tool in comprehensively and deeply understanding the photoelect...

Design of assembled composite of Mn3O4@Graphitic carbon porous nano-dandelions: A catalyst for Low–temperature selective catalytic reduction of NOx with remarkable SO2 resistance

The biggest challenge for selective catalytic reduction (SCR) of NO by NH3 at low temperatures is to develop robust catalysts with high resistance to SO2. Mn-based catalysts have attracted great attention for their excellent activity, but the poor SO2 resistance limits their application. Herein, we report a novel assembled composite featuring Mn3O4 nanoparticles embedded in defect-abundant graphitic carbon frame (Mn3O4@G-A) via a confinement–pyrolysis–oxidation strategy derived from MOF. The Mn3O4@G-A exhibits excellent activity (reaching over 90 % NO conversion in 100, 000 h−1 GHSV at 160 °C) and significantly improved SO2 resistance in comparison to pristine Mn3O4, and all the performance tests were conducted with 5.6 vol.% water vapor. By combining synchrotron radiation-based X-ray absorption spectroscopy and density functional theory calculation, we further discovered the positive role and the origin of graphitic carbon for improving SO2 resistance. Over the Mn3O4@G-A sample, the electrons can be transferred from graphitic carbon to Mn3O4 nanoparticles, which can regulate the electronic properties and oxidizing ability of Mn3O4 nanoparticles. The proper oxidizing ability of Mn3O4@G-A can inhibit the oxidation of SO2 to SO3, thus further avoid the formation of NH4HSO4 and improve the SO2 resistance. Our work here not only solves the current problem of poor SO2 resistance of Mn-based catalysts, but also provides new insights into the design and synthesis of MOF-derived graphitic carbon-containing catalysts for SCR applications.

Synchrotron Radiation-based X-ray phase-contrast imaging of the aortic walls in acute aortic dissection

ObjectiveSynchrotron radiation-based X-ray phase-contrast tomography (XPCT) imaging is an innovative modality for the quantitative analysis of three-dimensional morphology. XPCT has been used in this study to evaluate ascending aorta specimens from patients with acute type A aortic dissection (ATAAD) and to analyze the morphologic structure of the aortic wall in patients with this condition. MethodsAortic specimens from 12 patients were obtained during repairs for ATAAD and were fixed with formalin. Five patients had Marfan syndrome (MFS), and seven did not. In addition, six normal aortas were obtained from autopsies. Using XPCT (effective pixel size, 12.5 μm; density resolution, 1 mg/cm3), the density of the tunica media (TM) in each sample was measured at eight points. The specimens were subsequently analyzed pathologically. ResultsThe density of the TM was almost constant within each normal aorta (mean, 1.081 ± 0.001 g/cm3). The mean density was significantly lower in the ATAAD aortas without MFS (1.066 ± 0.003 g/cm3; P < .0001) and differed significantly between the intimal and adventitial sides (1.063 ± 0.003 vs 1.074 ± 0.002 g/cm3, respectively; P < .0001). The overall density of the TM was significantly higher in the ATAAD aortas with MFS than those without MFS (1.079 ± 0.008 g/cm3; P = .0003), and greater variation and markedly different distributions were observed in comparison with the normal aortas. These density variations were consistent with the pathologic findings, including the presence of cystic medial necrosis and malalignment of the elastic lamina in the ATAAD aortas with and without MFS. ConclusionsXPCT exhibited differences in the structure of the aortic wall in aortic dissection specimens with and without MFS and in normal aortas. Medial density was homogeneous in the normal aortas, markedly varied in those with MFS, and was significantly lower and different among those without MFS. These changes may be present in the TM before the onset of aortic dissection.

In Situ Formation of Hierarchical Bismuth Nanodots/Graphene Nanoarchitectures for Ultrahigh-Rate and Durable Potassium-Ion Storage.

Metallic bismuth (Bi) has been widely explored as remarkable anode material in alkali-ion batteries due to its high gravimetric/volumetric capacity. However, the huge volume expansion up to ≈406% from Bi to full potassiation phase K3 Bi, inducing the slow kinetics and poor cycling stability, hinders its implementation in potassium-ion batteries (PIBs). Here, facile strategy is developed to synthesize hierarchical bismuth nanodots/graphene (BiND/G) composites with ultrahigh-rate and durable potassium ion storage derived from an in situ spontaneous reduction of sodium bismuthate/graphene composites. The in situ formed ultrafine BiND (≈3 nm) confined in graphene layers can not only effectively accommodate the volume change during the alloying/dealloying process but can also provide high-speed channels for ionic transport to the highly active BiND. The BiND/G electrode provides a superior rate capability of 200 mA h g-1 at 10 A g-1 and an impressive reversible capacity of 213 mA h g-1 at 5 A g-1 after 500 cycles with almost no capacity decay. An operando synchrotron radiation-based X-ray diffraction reveals distinctively sharp multiphase transitions, suggesting its underlying operation mechanisms and superiority in potassium ion storage application.

Investigating tool engagement in groundwood pulping: finite element modelling and in-situ observations at the microscale

Abstract With industrial groundwood pulping processes relying on carefully designed grit surfaces being developed for commercial use, it is increasingly important to understand the mechanisms occurring in the contact between wood and tool. We present a methodology to experimentally and numerically analyse the effect of different tool geometries on the groundwood pulping defibration process. Using a combination of high-resolution experimental and numerical methods, including finite element (FE) models, digital volume correlation (DVC) of synchrotron radiation-based X-ray computed tomography (CT) of initial grinding and lab-scale grinding experiments, this paper aims to study such mechanisms. Three different asperity geometries were studied in FE simulations and in grinding of wood from Norway spruce. We found a good correlation between strains obtained from FE models and strains calculated using DVC from stacks of CT images of initial grinding. We also correlate the strains obtained from numerical models to the integrity of the separated fibres in lab-scale grinding experiments. In conclusion, we found that, by modifying the asperity geometries, it is, to some extent, possible to control the underlying mechanisms, enabling development of better tools in terms of efficiency, quality of the fibres and stability of the groundwood pulping process.

In Situ Structural Characterization of Functionally Graded Ni–Ti Shape Memory Alloy During Tensile Loading

A functionally graded NiTi shape memory alloy wire was investigated by in situ synchrotron radiation-based X-ray diffraction (SR-XRD) during cyclic tensile deformation. The transformation temperatures were determined by DSC and the thermomechanical behaviour was analysed by three-point bending test. The present study focussed on the localized heat treatment (Joule heat effect, reaching 300 °C, 350 and 400 °C pulses for 10 min) of NiTi wires, using an equipment that allows a large variety of graded conditions. Structural, mechanical and thermomechanical characterization is presented to get a perspective of the different types of graded functionality. A combination of two strategies has been used for the in situ analysis by SR-XRD of the tensile tests: (i) continuously following the structural evolution at one single point (at the center of the heat-treated segment) all long the load/unload cycle and (ii) scanning the full heat-treated segmentat previously defined discrete steps of the stress–strain curve. The combined information from both types of tests provided detailed information about the phase transformations taking place in different regions of the functionally graded segment, at different steps of the tensile load/unload cycle, giving a better understanding of the overall mechanical, namely the evidence of the sequence B2 ↔ R ↔ B19′ for the direct and reverse transformations.

On the Schmid's Law for the electric current-induced deformation: An in situ EBSD study

For metals and alloys, electric currents may induce atomic diffusion and morphological changes, known as the electromigration (EM) effect. Here we report the first direct application of conventional solid mechanics’ theory to predict the electric current-induced deformations based on the in situ electron backscattered diffraction and synchrotron radiation-based X-ray diffraction analyses of Cu strips under current stressing. At a given current density, the electric current-induced elastic, slip, or slip accompanying with twinning deformation in Cu strips was revealed. The Schmid's Law is well elucidating the occurrence of the electric current-induced plastic deformations, namely the slip and twinning ones. The study unveils that the electric current-induced strain and deformation can be described in the same context as for the conventional solid mechanics.

Tooth replacement in early sarcopterygians.

Teeth were an important innovation in vertebrate evolution but basic aspects of early dental evolution remain poorly understood. Teeth differ from other odontode organs, like scales, in their organized, sequential pattern of replacement. However, tooth replacement patterns also vary between the major groups of jawed vertebrates. Although tooth replacement in stem-osteichthyans and extant species has been intensively studied it has been difficult to resolve scenarios for the evolution of osteichthyan tooth replacement because of a dearth of evidence from living and fossil sarcopterygian fishes. Here we provide new anatomical data informing patterns of tooth replacement in the Devonian sarcopterygian fishes Onychodus, Eusthenopteron and Tiktaalik and the living coelacanth Latimeria based on microfocus- and synchrotron radiation-based X-ray microtomography. Early sarcopterygians generated replacement teeth on the jaw surface in a pattern similar to stem-osteichthyans, with damaged teeth resorbed and replacement teeth developed on the surface of the bone. However, resorption grades and development of replacement teeth vary spatially and temporally within the jaw. Particularly in Onychodus, where teeth were also shed through anterior rotation and resorption of bone at the base of the parasymphyseal tooth whorl, with new teeth added posteriorly. As tooth whorls are also present in more stem-osteichthyans, and statodont tooth whorls are present among acanthodians (putative stem-chondrichthyans), rotational replacement of the anterior dentition may be a stem-osteichthyan character. Our results suggest a more complex evolutionary history of tooth replacement.

Synthesis and Characterisation of Hierarchically Structured Titanium Silicalite-1 Zeolites with Large Intracrystalline Macropores.

The successful synthesis of hierarchically structured titanium silicalite-1 (TS-1) with large intracrystalline macropores by steam-assisted crystallisation of mesoporous silica particles is reported. The macropore topology was imaged in 3D by using electron tomography and synchrotron radiation-based ptychographic X-ray computed tomography, revealing interconnected macropores within the crystals accounting for about 30 % of the particle volume. The study of the macropore formation mechanism revealed that the mesoporous silica particles act as a sacrificial macropore template during the synthesis. Silicon-to-titanium ratio of the macroporous TS-1 samples was successfully tuned from 100 to 44. The hierarchically structured TS-1 exhibited high activity in the liquid phase epoxidation of 2-octene with hydrogen peroxide. The hierarchically structured TS-1 surpassed a conventional nano-sized TS-1 sample in terms of alkene conversion and showed comparable selectivity to the epoxide. The flexible synthesis route described here can be used to prepare hierarchical zeolites with improved mass transport properties for other selective oxidation reactions.

A Mechanism Study of Structural Transition of Lithium Vanadium Phosphate during the 1st Charge/Discharge in Comparison to Ti-Doped One

Battery is one of the most attractive energy storage systems for its usefulness in energy conversion in these days. A great attention has been paid to the Li-ion batteries, and a lot of attempts to develop the system exhibiting higher energy density and higher safety have been tried for many years. However, the safety of Li-ion battery has been problems continuously while the energy density has developed largely. The safety issues of Li-ion battery generally come from thermal runaway, mainly derived from oxygen evolution from cathode materials. Phosphate materials including frames of PO4 polyanions such as LiFePO4 are regarded as a suitable cathode material in Li-ion battery in terms of the point of view. Lithium vanadium phosphate (LVP) has high expectations as a cathode material because of its higher operating voltage (~3.6V) and theoretical capacity(197mAh/g) compared to LiFePO4. While monoclinic LVP has a higher energy density, large hysteresis comes from asymmetric charge/discharge profile, and capacity fading are the main problems when three lithium ions are extracted by raising the voltage up to 4.8V. To overcome these limitations, fine studies about the mechanism have been carried out by a few groups. Although the mechanism studies were carried out by L. Nazar group about structural transition [1] and by Lee and Park about the possible pathway of lithium ion in the structure [2], representatively, the reasons for capacity fading on LVP should be studied more. In this work, we investigated the structural changes of LVP during the first charge and discharge process of voltage window of 3.0V to 4.8V by using Galvanostatic Intermittent Titration Technique (GITT), synchrotron radiation-based X-ray Absorption Spectroscopy (XAS) and in situ X-ray diffraction (XRD). The irreversible structural transitions between charge and discharge process are one of the possible reason for the capacity fading. Also, we conducted comparison study on the electrochemical and structural properties between LVP and Li3Ti0.03V1.97(PO4)3/graphene (LVP-Ti) to overcome limitations of LVP. In situ XRD patterns show four consecutive two-phase transitions on LVP during the charge process. During the reinsertion of lithium ion, the patterns of LVP look like a combined process of single solid solution and two-phase transitions between full charged LVP (FC-LVP) and Li2V2(PO4)3 (Li2 phase) without forming Li1V2(PO4)3. In GITT data, a two phase transition behavior which was previously reported as a solid solution behavior during the Li-ion insertion from full charged LVP to Li2 phase in the discharge process is observed. From these data, it can be said that transforming behavior from FC-LVP to Li2 phase is closer to two-phase reaction. In LVP-Ti case, the charge capacity was 185.84 mAh/g and the discharge capacity was 171.20 mAh/g in the first cycle, which were higher than those of LVP, 178.84 mAh/g and 162.99 mAh/g. And in situ XRD patterns show four consecutive two-phase transitions as in LVP. During the phase transition in charge/discharge, LVP-Ti faces less lattice mismatch than LVP, resulting in better electrochemical performance, and this phenomenon is originated from smaller particle size and enduring strain. The XAS result shows that the XANES peaks of LVP-Ti change gradually which is in line with the XRD result as same as in LVP case. However, the larger peak area of the pre-edge for LVP-Ti suggesting that more electrons were released upon charging. This means that the higher capacities of LVP-Ti is contributed by further utilization of the V redox reaction. [1] Yin, S-C., Hiltrud Grondey, Pierre Strobel, M. Anne, and Linda F. Nazar. "Electrochemical property: structure relationships in monoclinic Li3-yV2(PO4)3." Journal of the American Chemical Society 125, no. 34 (2003): 10402-10411. [2] Lee, S., & Park, S. S. (2012). Atomistic simulation study of monoclinic Li3V2(PO4)3 as a cathode material for lithium ion battery: structure, defect chemistry, lithium ion transport pathway, and dynamics. The Journal of Physical Chemistry C, 116(48), 25190-25197.