Advanced Synchrotron Radiation Research Articles

N-methyl Formamide Electrolyte Additive Enabling Highly Reversible Zn Anodes.

Parasitic side reactions and dendrites formation hinder the application of aqueous zinc ion batteries due to inferior cycling life and low reversibility. Against this background, N-methyl formamide (NMF), a multi-function electrolyte additive is applied to enhance the electrochemical performance. Studied via advanced synchrotron radiation spectroscopy and DFT calculations, the NMF additive simultaneously modifies the Zn2+ solvation structure and ensures uniform zinc deposition, thus suppressing both parasitic side reactions and dendrite formation. More importantly, an ultralong cycling life of 3115h in the Zn||Zn symmetric cell at a current density of 0.5mAcm-2 is achieved with the NMF additive. Practically, the Zn||PANI full cell utilizing NMF electrolyte shows better rate and cycling performance compared to the pristine ZnSO4 aqueous electrolyte. This work provides useful insights for the development of high-performance aqueous metal batteries.

A 5.12-Gbps serializer circuit for front-end fast readout electronics of silicon pixelated detectors

Advanced synchrotron radiation sources are major facilities for analyzing the formation and evolution of material structure in multidisciplinary research, owing to their high luminosity, low emittance, wide energy bandwidth and other characteristics. In China, several advanced synchrotron radiation sources are under construction, including the HEPS (High Energy Photon Source) and SHINE (Shanghai high repetition rate X-ray Free Electron Laser and extreme light facility). These facilities are poised to become major multidisciplinary research platforms in China. To meet the requirements of pixel detectors in these facilities, dedicated pixel readout chips are being developed, including HEPS-BPIX and HYLITE. This paper presents a high-speed serializer circuit developed in a commercial 130-nm CMOS technology for the full-scale (128 × 128) pixel readout chip of HYLITE, which requires a data rate of 4 Gbps currently. The serializer consists of a 16-to-1 binary-tree multiplexer, a ring-oscillating-based phase-locked loop (RO-PLL) and a current-mode logic driving stage with a multi-stage pre-amplifier. Test results demonstrate its expected functionality within a wide operating range from 0.52 Gbps to 5.5 Gbps. At 5.12 Gbps, the measured jitter values are about 2 ps for random jitter, 20 ps for deterministic jitter, and 47 ps for total jitter with a 10−12 bit error rate. Additionally, the horizontal and vertical eye openings are 0.84 UI and 72%, respectively. These positive results indicate that the serializer meets the requirements of HYLITE.

Bimodal design of 500MHz and 1.5GHz normal conducting RF cavity for advanced synchrotron radiation facilities

The advanced storage ring light source needs to realize ultra-low emissivity beam operation, and improving the Touschek lifetime puts forward higher requirements for the performance of RF cavity. In this paper, a novel bimodal normal conducting RF cavity is proposed. In one cavity, two power sources will be connected at the same time to realize the simultaneous operation of the two frequencies. The TM010 mode with the frequency of 500 MHz is used for acceleration, and the TM020 mode with the frequency of 1.5 GHz is used as the third harmonic to improve the height of the RF bucket and achieve the purpose of lengthening the beam bunch. Two couplers are designed to adapt to the working characteristics of bimodal RF cavity.

Structure regulation and synchrotron radiation investigation of cathode materials for aqueous Zn-ion batteries.

In view of the advantages of low cost, environmental sustainability, and high safety, aqueous Zn-ion batteries (AZIBs) are widely expected to hold significant promise and increasingly infiltrate various applications in the near future. The development of AZIBs closely relates to the properties of cathode materials, which depend on their structures and corresponding dynamic evolution processes. Synchrotron radiation light sources, with their rich advanced experimental methods, serve as a comprehensive characterization platform capable of elucidating the intricate microstructure of cathode materials for AZIBs. In this review, we initially examine available cathode materials and discuss effective strategies for structural regulation to boost the storage capability of Zn2+. We then explore the synchrotron radiation techniques for investigating the microstructure of the designed materials, particularly through in situ synchrotron radiation techniques that can track the dynamic evolution process of the structures. Finally, the summary and future prospects for the further development of cathode materials of AZIBs and advanced synchrotron radiation techniques are discussed.

放射光回折システムの高機能化と機能性材料の開発研究

Driven by improvement of the computer speed and tremendous efforts of crystallographers and equipment manufacturers, X-ray structure analysis has recently become relatively easy and requires no specialized knowledge. On the other hand, synchrotron radiation diffraction experiments have mainly aimed at advanced structural analysis, including electron density analysis, taking advantage of stable and intense X-rays. In recent years, demand for the use of the facility in the materials field has increased, but researchers unfamiliar with synchrotron radiation experiments have felt difficulty in use. Based on my experience in developing conventional diffractometers and software at the equipment manufacturer where I worked after obtaining my degree, I have promoted the development of advanced synchrotron radiation X-ray diffraction systems at SPring-8, a large synchrotron radiation facility. In particular, I have been responsible for the single crystal structure analysis beamline（BL02B1）and the powder diffraction beamline（BL02B2）, which have a wide range of user groups and diverse requirements for instrumental performance, and engaged in instrument development. In addition, I have also worked on structural analysis of functional materials and clarified their structure-function relationships. Among them, I introduce fruitful results on generation process of magnesia cement and design of spin crossover Fe（II）complexes. I believe that such upgrading of synchrotron radiation diffraction systems and development research of functional materials could not be performed without hardware and software knowledge which I learned at the equipment manufacturer.

Study on myocardial toxicity induced by lead halide perovskites nanoparticles

Lead halide perovskites (LHPs) are outstanding candidates for next-generation optoelectronic materials, with considerable prospects of use and commercial value. However, knowledge about their toxicity is scarce, which may limit their commercialization. Here, for the first time, we studied the cardiotoxicity and molecular mechanisms of representative CsPbBr3 nanoparticles in LHPs. After their intranasal administration to Institute of Cancer Research (ICR) mice, using advanced synchrotron radiation, mass spectrometry, and ultrasound imaging, we revealed that CsPbBr3 nanoparticles can severely affect cardiac systolic function by accumulating in the myocardial tissue. RNA sequencing and Western blotting demonstrated that CsPbBr3 nanoparticles induced excessive oxidative stress in cardiomyocytes, thereby provoking endoplasmic reticulum stress, disturbing calcium homeostasis, and ultimately leading to apoptosis. Our findings highlight the cardiotoxic effects of LHPs and provide crucial toxicological data for the product.

CsPbBr3 Perovskite Nanoparticles causes Colitis-Like Symptom via Promoting Intestinal Barrier Damage and Gut Microbiota Dysbiosis.

Lead-based perovskite nanoparticles (Pb-PNPs) with superior optoelectronic properties are promising alternatives for the next generation of photovoltaics materials. This raises a great concern about their potential exposure toxicity in biological systems. However, little is known about their adverse effects on the gastrointestinal tract system so far. Here, the aim is to investigate the biodistribution, biotransformation, potential gastrointestinal tract toxicity, and effect on the gut microbiota after oral exposure to the CsPbBr3 perovskite nanoparticles (CPB PNPs). The advanced synchrotron radiation based microscopic X-ray fluorescence scanning and X-ray absorption near-edge spectroscopy demonstrate that high doses of CPB (CPB-H) PNPs can gradually transform into different lead-based compounds, subsequently accumulating in the gastrointestinal tract, especially the colon. Meanwhile, the pathological changes of stomach, small intestine, and colon reveal that CPB-H PNPs have higher gastrointestinal tract toxicity than Pb(Ac)2 , consequently leading to colitis-like symptoms. More importantly, 16S rRNA gene sequencing analysis discloses that CPB-H PNPs cause more significant alterations in the richness and diversity of the gut microbiota related to inflammation, intestinal barrier, and immune function than Pb(Ac)2 . The findings may contribute to shedding light on understanding the adverse effects on gastrointestinal tract and gut microbiota of Pb-PNPs.

Field test study for evaluation of vibration control capacity of cracked mass concrete layer

Passive control is typically implemented to regulate ground vibration in advanced ultra-precision and large-scale synchrotron radiation facilities. This paper presents the field test to evaluate the influence of cracks on the vibration control capacity of a mass concrete layer used as a passive control method of an advanced synchrotron radiation facility. Simplified finite element model (FEM) analysis is utilized to simulate the cracks and analyze the key factor that influences the vibration control capacity of the mass concrete layer. In the field test, cracks are artificially formed by creating cuts in two orthometric directions on the surface of a 3-m-thick concrete layer. Measurement points and a vibrator capable of generating simple harmonic excitation (1–100 Hz) are positioned along a straight line. Velocity signals vertical to the ground are obtained to study the vibration attenuation in the vertical direction. Test results indicate that the velocity signals on the concrete layer are sensitive to the cracks; the vibration control ability of the concrete layer is slightly affected by the depth, length and location of the cracks in the frequency band of 1–100 Hz. The proposed simplified FEMs can reflect the cracked concrete layer’s vibration control ability from 1 to 100 Hz. Numerical study results indicate that the thickness of the concrete layer rather than the density or elastic modulus is the key factor in vibration control ability.

Neurotoxicity study of lead-based perovskite nanoparticles

Lead-based halide perovskite nanoparticles (Pb-PNPs) are promising alternatives for the next-generation of optoelectronic materials, while their nonnegligible biological behavior after exposure are still an enigma. Here, we clarify the translocation, biotransformation, and biodistribution related neurotoxicity of representative CsPbBr3 PNPs in C57BL/6J mice after intranasal administration through a combination of the feat of advanced synchrotron radiation (SR) and traditional analytical techniques. SR-based microscopic X-ray fluorescence scanning, inductively coupled plasma mass spectrometry and behavioral data demonstrate that CsPbBr3 PNPs can be transported and accumulated in the hippocampus, easily triggering Ca overload, causing severe damage of hippocampus-dependent learning, memory, and cognition behavior. Meanwhile, SR–based X-ray absorption near-edge spectroscopy analysis also reveals that CsPbBr3 PNPs can transform into soluble and insoluble lead compounds in different physiological environments. The toxicity of CsPbBr3 PNPs is higher than that of soluble Pb(Ac)2 due to the sustained release of Pb ions. The CsPbBr3 PNPs cause nerve cell apoptosis through triggering intracellular Ca2+ overload, upregulating reactive oxygen species production, while disordering the mitochondrial membrane potential. Our work provides significant insights into the neurological effects and mechanism of Pb-PNPs.

Beam orbit shift due to BPM thermal deformation using machine learning

Stabilizing beam orbit is critical for advanced synchrotron radiation light sources. The beam orbit can be affected by many sources. To maintain a good orbit stability, global orbit feedback systems (OFB) has been widely used. However, the BPM thermal deformation would lead to BPM misreading, which can not be handled by OFB. Usually, extra diagnostics, such as position transducers, is needed to measure the deformation dependency of BPM readings. Here, an alternative approach by using the machine operation historic data, including BPM temperature, insertion device (ID) gaps and corrector currents, is presented. It is demonstrated at Hefei Light Source (HLS). The average orbit shift due to BPM thermal deformation is about 34.5 μm/°C (horizontal) and 20.0 μm/°C (vertical).

Spin orbit torque driven magnetization reversal in CoFeTaB/Pt probed by resonant x-ray reflectivity

When electrical current flows through a heavy metal layer adjacent to a ferromagnetic layer, a spin-orbit torque is exerted on the magnetic spins within the ferromagnetic layer. This link between electronics and magnetic materials is significant for the development of novel technological memory and processing devices in a field known as spintronics. Here, the authors show how advanced synchrotron radiation techniques provide a new, nondestructive, and $i\phantom{\rule{0}{0ex}}n$ $s\phantom{\rule{0}{0ex}}i\phantom{\rule{0}{0ex}}t\phantom{\rule{0}{0ex}}u$ view of the current-driven layer-dependent magnetization reversal in a spintronic bilayer system.

Development of a novel high gradient quadrupole magnet

High gradient quadrupoles are key components for advanced synchrotron radiation light sources. This paper presents the magnet design, the mechanical structure and the magnetic field measurements of a novel high gradient quadrupole magnet. This high gradient quadrupole magnet with a gradient greater than 100 T/m uses permanent magnets (PMs) on the poles to improve the excitation efficiency. The magnetic field measurement results show the feasibility of this magnetic design.

Research progress on speciation analysis of arsenic in traditional Chinese medicine

Abstract Traditional Chinese medicine contains arsenic (As), which in the natural environment accumulates in plants during the growth of Chinese medicinal materials; there are mineral medicines containing As in Chinese patent medicine such as As4S4, As2S3, etc. Due to the toxicity of As-containing compounds and its role in inflammation and treatment of cancers such as leukemia, it is necessary to analyze the chemical form of As. A comprehensive investigation of the compound forms of heavy metals rather than the simple total amount of elements will lay the foundation for the scientific and objective evaluation of the safety of heavy metals. This article summarizes the speciation of As in bulk Chinese medicinal materials and Chinese patent medicines in recent years, and reviews the main research methods of As speciation analysis. The separation and detection combined analysis method focuses on the high-performance liquid chromatography-plasma mass spectrometry and high-performance liquid chromatography-hydride generation-atomic fluorescence spectroscopy, etc. Taking the advanced synchrotron radiation source as the research platform, the use of X-ray near edge absorption fine structure spectrum and micro-area X-ray fluorescence analysis as a microscopic analysis technique supports direct analysis of the As speciation in situ. It is the most promising morphological analysis method.

Operando X-ray study of service behavior of catalytic materials based on synchrotron radiation

Considering the energy and environmental issues faced by human society, hydrogen has become increasingly important, and electrocatalytic water splitting is considered to be an ideal way to solve these energy issues. However, although most electrocatalysts will undergo a structural evolution when in service conditions, our understanding of the service behavior of catalysts is limited. To design highly active catalysts, operando characterization techniques must be used to study their dynamic structural evolution. Today, the development of synchrotron radiation devices has reached an important stage. Synchrotron-radiation-based X-ray characterization, which has high energy, large flux, and excellent collimation compared with the ordinary laboratory X-ray source, can capture the precise structure of catalytic materials. In this review, we present the development status of synchrotron radiation devices and the basic principles of operando X-ray absorption spectroscopy, X-ray diffraction spectroscopy, and X-ray photoelectron spectroscopy based on synchrotron radiation. In addition, we highlight studies related to the dynamic service behavior of water-splitting catalysts under real conditions and list a variety of operando studies of typical water-splitting catalysts, including NiFe hydroxide/(oxy)hydroxides, perovskite oxides, spinel oxides, and noble-metal-based catalysts. The use of operando X-ray techniques deepens our understanding of the catalyst reaction mechanism and provides a basis for identifying the dynamic structure–performance correlation of catalysts. We summarize the problems and challenges of operando X-ray-based techniques in complex electrochemical environments and propose the prospect of an advanced synchrotron radiation facility for operando X-ray characterization. With the development of the next-generation synchrotron radiation facility, adequately using this advanced X-ray light source to study the dynamic structure–activity correlation of catalytic materials throughout their life cycle to achieve the precise design and synthesis of complex pre-catalysts will advance the development of this field by enabling greater refinement and control.

An unprecedented insight into the catalytic mechanism of copper nitrite reductase from atomic-resolution and damage-free structures.

Copper-containing nitrite reductases (CuNiRs), encoded by nirK gene, are found in all kingdoms of life with only 5% of CuNiR denitrifiers having two or more copies of nirK Recently, we have identified two copies of nirK genes in several α-proteobacteria of the order Rhizobiales including Bradyrhizobium sp. ORS 375, encoding a four-domain heme-CuNiR and the usual two-domain CuNiR (Br 2DNiR). Compared with two of the best-studied two-domain CuNiRs represented by the blue (AxNiR) and green (AcNiR) subclasses, Br 2DNiR, a blue CuNiR, shows a substantially lower catalytic efficiency despite a sequence identity of ~70%. Advanced synchrotron radiation and x-ray free-electron laser are used to obtain the most accurate (atomic resolution with unrestrained SHELX refinement) and damage-free (free from radiation-induced chemistry) structures, in as-isolated, substrate-bound, and product-bound states. This combination has shed light on the protonation states of essential catalytic residues, additional reaction intermediates, and how catalytic efficiency is modulated.

Anomalous self-optimization of sulfate ions for boosted oxygen evolution reaction

Broadly, the oxygen evolution reaction (OER) has been deeply understood as a significant part of energy conversion and storage. Nevertheless, the anions in the OER catalysts have been neglected for various reasons such as inactive sites, dissolution, and oxidation, amongst others. Herein, we applied a model catalyst s-Ni(OH)2 to track the anionic behavior in the catalyst during the electrochemical process to fill this gap. The advanced operando synchrotron radiation Fourier transform infrared (SR-FTIR) spectroscopy, synchrotron radiation photoelectron spectroscopy (SRPES) depth detection and differential X-ray absorption fine structure (Δ-XAFS) spectrum jointly point out that some oxidized sulfur species (SO42−) will self-optimize new Ni–S bonds during OER process. Such amazing anionic self-optimization (ASO) behavior has never been observed in the OER process. Subsequently, the optimization-derived component shows a significantly improved electrocatalytic performance (activity, stability, etc.) compared to reference catalyst Ni(OH)2. Theoretical calculation further suggests that the ASO process indeed derives a thermodynamically stable structure of the OER catalyst, and then gives its superb catalytic performance by optimizing the thermodynamic and kinetic processes in the OER, respectively. This work demonstrates the vital role of anions in the electrochemical process, which will open up new perspectives for understanding OER and provide some new ideas in related fields (especially catalysis and chemistry).

Thermal stress-induced charge and structure heterogeneity in emerging cathode materials

Nickel-rich layered oxide cathode materials are attractive near-term candidates for boosting the energy density of next generation lithium-ion batteries. The practical implementation of these materials is, however, hindered by unsatisfactory capacity retention, poor thermal stability, and oxygen release as a consequence of structural decomposition, which may have serious safety consequences. The undesired side reactions are often exothermic, causing complicated electro-chemo-mechanical interplay at elevated temperatures. In this work, we explore the effects of thermal exposure on chemically delithiated LiNi0.8Mn0.1Co0.1O2 (NMC-811) at a practical state-of-charge (50% Li content) and an over-charged state (25% Li content). A systematic study using a suite of advanced synchrotron radiation characterization tools reveals the dynamics of thermal behavior of the charged NMC-811, which involves sophisticated structural and chemical evolution; e.g. lattice phase transformation, transition metal (TM) cation migration and valence change, and lithium redistribution. These intertwined processes exhibit a complex 3D spatial heterogeneity and, collectively, form a valence state gradient throughout the particles. Our study sheds light on the response of NMC-811 to elevated temperature and highlights the importance of the cathode’s thermal robustness for battery performance and safety.

Detect molecular spectral features of newly developed Vicia faba varieties and protein metabolic characteristics in ruminant system using advanced synchrotron radiation based infrared microspectroscopy: A preliminary study.

Recently, advanced synchrotron radiation-based Fourier transform infrared microspectroscopy (SR-IMS) has been developed as a rapid, direct, non-destructive and bioanalytical technique. To date, there has been very little application of this technique to study the molecular structure make-up in pulse seeds. Thus, the objectives of this study were to detect the interactive association between protein molecular structure and nutrient availability of newly developed Vicia faba varieties. Two different varieties of faba beans (CDC Snowdrop = low-tannin variety; vs. FB9-4 = high-tannin variety) were selected for this study. The molecular spectra data were collected by using SR-IMS. The ratio of both amide I to II area and height were higher (P < 0.01), while the ratio of α-helix to β-sheet was lower (P < 0.05) in CDC Snowdrop compared to FB9-4. The crude protein (CP) content and the predicted truly digestible nutrients as well as the bioenergy values did not vary between two varieties. The CDC Snowdrop had exhibited a higher (P < 0.01) rapidly degradable CP fraction (75.99 vs. 71.45% on CP) and a lower (P < 0.01) moderately degradable CP fraction (19.43 vs. 22.85% on CP), resulting in a higher (P < 0.01) rumen degradable protein and a lower (P < 0.01) rumen undegradable protein content than that of FB9-4 variety. However, the total supply of digestible rumen undegraded feed protein was higher (P < 0.05) in FB9-4 than CDC Snowdrop. Strong positive correlations were found between the ratio of α-helix to β-sheet and CP contents (R = 0.86, P < 0.01) as well as the truly digestible CP contents (R = 0.83, P < 0.01); respectively. In conclusion, the results of this study reveal that the protein are metabolized differently between different type of faba bean varieties and the advanced SR-IMS molecular spectroscopy can be used to rapidly delineate protein molecular structure motifs along with their nutritive value in ruminant livestock system.

Biocompatible Materials Based on Self-Assembling Peptides on Ti25Nb10Zr Alloy: Molecular Structure and Organization Investigated by Synchrotron Radiation Induced Techniques.

In this work, we applied advanced Synchrotron Radiation (SR) induced techniques to the study of the chemisorption of the Self Assembling Peptide EAbuK16, i.e., H-Abu-Glu-Abu-Glu-Abu-Lys-Abu-Lys-Abu-Glu-Abu-Glu-Abu-Lys-Abu-Lys-NH2 that is able to spontaneously aggregate in anti-parallel β-sheet conformation, onto annealed Ti25Nb10Zr alloy surfaces. This synthetic amphiphilic oligopeptide is a good candidate to mimic extracellular matrix for bone prosthesis, since its β-sheets stack onto each other in a multilayer oriented nanostructure with internal pores of 5–200 nm size. To prepare the biomimetic material, Ti25Nb10Zr discs were treated with aqueous solutions of EAbuK16 at different pH values. Here we present the results achieved by performing SR-induced X-ray Photoelectron Spectroscopy (SR-XPS), angle-dependent Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, FESEM and AFM imaging on Ti25Nb10Zr discs after incubation with self-assembling peptide solution at five different pH values, selected deliberately to investigate the best conditions for peptide immobilization.

Chemical and kinetic insights into the Thermal Decomposition of an Oxide Layer on Si(111) from Millisecond Photoelectron Spectroscopy

Despite thermal silicon oxide desorption is a basic operation in semiconductor nanotechnology, its detailed chemical analysis has not been yet realized via time-resolved photoemission. Using an advanced acquisition system and synchrotron radiation, heating schedules with velocities as high as 100 K.s−1 were implemented and highly resolved Si 2p spectra in the tens of millisecond range were obtained. Starting from a Si(111)-7 × 7 surface oxidized in O2 at room temperature (1.4 monolayer of oxygen), changes in the Si 2p spectral shape enabled a detailed chemical analysis of the oxygen redistribution at the surface and of the nucleation, growth and reconstruction of the clean silicon areas. As desorption is an inhomogeneous surface process, the Avrami formalism was adapted to oxide desorption via an original mathematical analysis. The extracted kinetic parameters (the Avrami exponent equal to ~2, the activation energy of ~4.1 eV and a characteristic frequency) were found remarkably stable within a wide (~110 K) desorption temperature window, showing that the Avrami analysis is robust. Both the chemical and kinetic information collected from this experiment can find useful applications when desorption of the oxide layer is a fundamental step in nanofabrication processes on silicon surfaces.