A seven-crystal spectrometer for high-energy resolution X-ray spectroscopy at Shanghai Synchrotron Radiation Facility

A Johann-type X-ray spectrometer was successfully developed at the hard X-ray branch(in-vacuum undulator with a 24-mm periodic length)of the energy material beamline(E-line)at the Shanghai Synchrotron Radiation Facility(SSRF).This spectrometer was utilized to implement X-ray emission spectroscopy(XES),high-energy resolution fluorescence-detected X-ray absorption spectroscopy(HERFD-XAS),and resonant inelastic X-ray scattering.Seven spherically bent crystals were positioned on the respective vertical 500-mm-diameter Rowland circles,adopting an area detector to increase the solid angle to 1.75%of 4πsr,facilitating the study of low-concentrate systems under complex reaction conditions.Operated under the atmosphere pressure,the spectrometer covers the energy region from 3.5 to 18 keV,with the Bragg angle ranging from 73°to 86°during vertical scanning.It offers a promised energy resolution of sub-eV(XES)and super-eV(HERFD-XAS).Generally,these comprehensive core-level spectroscopy methods based on hard X-rays at the E-line with an extremely high photon flux can meet the crucial requirements of a green energy strategy.Moreover,they provide substantial support for scientific advances in fundamental research.

Towards adaptable synchrotron image restoration pipeline

Synchrotron microscopic data commonly suffer from poor image quality with degraded resolution incurred by instrumentation defects or experimental conditions.Image restoration methods are often applied to recover the reduced resolution,providing improved image details that can greatly facilitate scientific discovery.Among these methods,deconvolution techniques are straightforward,yet either require known prior information or struggle to tackle large experimental data.Deep learning(DL)-based super-resolution(SR)methods handle large data well,however data scarcity and model generalizability are problematic.In addition,current image restoration methods are mostly offline and inefficient for many beamlines where high data volumes and data complexity issues are encountered.To overcome these limitations,an online image-restoration pipeline that adaptably selects suitable algorithms and models from a method repertoire is promising.In this study,using both deconvolution and pretrained DL-based SR models,we show that different restoration efficacies can be achieved on different types of synchrotron experimental data.We describe the necessity,feasibility,and significance of constructing such an image-restoration pipeline for future synchrotron experiments.

Chemical Structure of HfO2/Si Interface with Angle-Resolved Synchrotron Radiation Photoemission Spectroscopy

Interracial chemical structure of HfO2/Si （100） is investigated using angle-resolved synchrotron radiation photoemission spectroscopy （ARPES）. The chemical states of Hf show that the Hf 4f binding energy changes with the probing depth and confirms the existence of Hf-Si-O and Hf Si bonds. The Si 2p spectra are taken to make sure that the interracial structure includes the Hf silicates, Hf silicides and SiOx. The metallic characteristic of the Hf-Si bonds is confirmed by the valence band spectra. The depth distribution model of this interface is established.

COPOLYMERS OF CHLOROETHYL METHACRYLATE, GLYCIDYL METHACRYLATE, AND METHYL METHACRYLATE AS SYNCHROTRON RADIATION x-RAY PHOTORESISTS

The copolymers of chloroethyl methacrylate (CMA), glycidyl methacrylate (GMA), and methyl methacrylate (MMA) were synthesized in benzene solution. Their breadths of the molecular weight distributions are 2.1 and 2.3, respectively. The thermal stability of P(GMA-CMA) is superior to that of P(CMA-MMA). The resolutions of P(CMA-MMA) and P(GMA-CMA) photoresists were found to be 0.1-0.16 mu m and 0.17-0.2 mu m, respectively. (Author abstract) 9 Refs.

Study on Atomic Fluorescence Spectrometry Excited by Synchrotron Radiation

A novel analysis approach using atomic fluorescence excited by synchrotron radiation is presented. A system for synchrotron radiation-atomic fluorescence spectrometry is developed, and experimental conditions such as flow rate, analyte acidity, concentration of pre-reducing and hydrogenation system are optimized. The proposed method is successfully applied to get an excitation spectrum of arsenic. Seven of ten primary spectral lines, four of which have never been reported by means of atomic fluorescence spectrometry, agree well with the existing reports. The other three are proposed for the first time. Excitation potentials and possible transitions are investigated. Especially for the prominent line at 234.99 nm, the mechanism of generation is discussed and a model of energy transition processes is proposed.

Synchrotron radiation VUV double photoionization of some small molecules

The VUV double photoionizations of small molecules （NO, CO, CO2, CS2, OSC and NH3） were investigated with photoionization mass spectroscopy using synchrotron radiation. The double ionization energies of molecules were determined with photoionization efficiency spectroscopy. The total energies of these molecules and their parent dications （NO^2＋,CO^2＋,CO2^2＋, CS2^2＋, OSC^2＋and NH^2＋） were calculated using the Gaussian O3 program and Gaussian 2 （NO^2＋, CO^2＋, CO2^2＋,CS2^2＋,OSC^2＋ and NH3^2＋） were calculated using the Gaussian 03 program and Gaussian 2 calculations. Then, the adiabatic double ionization energies of the molecules were predicated by using high accuracy energy mode. The experimental double ionization energies of these small molecules were all in reasonable agreement with their respective calculated adiabatic double ionization energies. The mechanisms of double photoionization of these molecules were discussed based on a comparison of our experimental results with those predicted theoretically. The equilibrium geometries and harmonic vibrational frequencies of molecules and their parent dications were calculated by using the MP2 （full） method. The differences in configurations between these molecules and their parent dications were also discussed on the basis of theoretical calculations.

Studies of the Gd Overlayer on Cr by Synchrotron Radiation Photoemission

The formation of Gd/Cr interface,the growth mechanism and electronic structure of Gd over-layers were investigated by synchrotron radiation photoemission.It is shown that Gd adatoms interact with the Cr substrate weakly.A lower deposition rate of the Gd overlayer(l.0Å/min)favors the smooth growth of Gd/Cr interface.However,higher deposition rate(6.0Å/min)leads to the cluster growth of the Gd overlayer and the presence of a“two-peak”feature of Gd 4f emission.We correlate this feature with the different coordination number of surface atoms derived from cluster-induced surface roughness.

Electronic Structure in Cd_(0.96)Zn_(0.04)Te Compound: A Synchrotron Radiation Photoemission Study

We have studied the electronic structure of clean CdZnTe(111)compound using high resolution synchrotron radiation photoemission spectroscopy.Surface states were found in Cd,Te 4d core levels and valence band.The valence band measurement is in good agreement with theoretical calculations using linear muffin-tin orbit method.

Energy band alignment of PbTe/CdTe(111) interface determined by ultraviolet photoelectron spectra using synchrotron radiation

The energy band structure with type-I alignment at the PbTe/CdTe（111） heterojunction interface is determined by the ultraviolet photoelectron spectrum using synchrotron radiation. The valence band and conduction band offsets are obtained to be 0.09±0.12 and 1.19±0.12 eV, respectively. These results are in agreement with theoretically predicted ones. The accurate determination of the valence band and conduction band offsets is useful for the fundamental understanding of the mid-infrared light emission from the PbTe/CdTe heterostructures and its application in devices.

Photoemission Studies of K-Promoted Nitridation of InP (100) Surface Using Synchrotron Radiation

The effect of molecular nitrogen exposure on the surfaces of InP(100)modified by potassium overlayers is investigated by core-level and valence-band photoemission spectroscopy using Synchrotron radiation.In comparison with InP(110)surface,we found the promotion is much stronger for InP(100)surface due to the central role of surface defects in the promotion;furthermore,in contrast with K-promoted oxidation of InP(100)where the bonding is observed between indium and oxygen,indium atoms did not react directly with nitrogen atoms during the K-promoted nitridation of InP(100).

Modulation of Electronic States in Bimetallic-doped Nitrogen-Carbon Based Nanoparticles for Enhanced Oxygen Reduction Kinetics

Controlling the local electronic structure of active ingredients to improve the adsorption desorption characteristics of oxygen-containing intermediates over the electrochemical liquid-solid interfaces is a critical challenge in the field of oxygen reduction reaction(ORR)catalysis.Here,we offer a simple approach for modulating the electronic states of metal nanocrystals by bimetal co-doping into carbon-nitrogen substrate,allowing us to modulate the electronic structure of catalytic active centers.To test our strategy,we designed a typical bimetallic nanoparticle catalyst(Fe-Co NP/NC)to flexibly alter the reaction kinetics of ORR.Our results from synchrotron Xray absorption spectroscopy and X-ray photoelectron spectroscopy showed that the co-doping of iron and cobalt could optimize the intrinsic charge distribution of Fe-Co NP/NC catalyst,promoting the oxygen reduction kinetics and ultimately achieving remarkable ORR activity.Consequently,the carefully designed Fe-Co NP/NC exhibits an ultra-high kinetic current density at the operating voltage(71.94 mA/cm^(2)at 0.80 V),and the half-wave potential achieves 0.915 V,which is obviously better than that of the corresponding controls including Fe NP/NC,Co NP/NC.Our findings provide a unique perspective for optimizing the electronic structure of active centers to achieve higher ORR catalytic activity and faster kinetics.

Quick-scanning X-ray absorption fine structure beamline at SSRF

The layout and characteristics of the hard X-ray spectroscopy beamline(BL11B)at the Shanghai synchrotron radiation facility are described herein.BL11B is a bending-magnet beamline dedicated to conventional and millisecond-scale quick-scanning X-ray absorption fine structures.It is equipped with a cylindrical collimating mirror,a double-crystal monochromator comprising Si(111)and Si(311),a channel-cut quick-scanning Si(111)monochromator,a toroidal focusing mirror,and a high harmonics rejection mirror.It can provide 5-30 keV of X-rays with a photon flux of~5×10^(11)photons/s and an energy resolution of~1.31×10^(-4)at 10 keV.The performance of the beamline can satisfy the demands of users in the fields of catalysis,materials,and environmental science.This paper presents an overview of the beamline design and a detailed description of its performance and capabilities.

Beam based alignment using a neural network

Beams typically do not travel through the magnet centers because of errors in storage rings.The beam deviating from the quadrupole centers is affected by additional dipole fields due to magnetic field feed-down.Beam-based alignment(BBA)is often performed to determine a golden orbit where the beam circulates around the quadrupole center axes.For storage rings with many quadrupoles,the conventional BBA procedure is time-consuming,particularly in the commissioning phase,because of the necessary iterative process.In addition,the conventional BBA method can be affected by strong coupling and the nonlinearity of the storage ring optics.In this study,a novel method based on a neural network was proposed to determine the golden orbit in a much shorter time with reasonable accuracy.This golden orbit can be used directly for operation or adopted as a starting point for conventional BBA.The method was demonstrated in the HLS-II storage ring for the first time through simulations and online experiments.The results of the experiments showed that the golden orbit obtained using this new method was consistent with that obtained using the conventional BBA.The development of this new method and the corresponding experiments are reported in this paper.

Overcoming the Na-ion conductivity bottleneck for the cost-competitive chloride solid electrolytes

Chloride solid electrolytes possess multiple advantages for the construction of safe,energy-dense allsolid-state sodium batteries,but presently the chlorides with sufficiently high cost-competitiveness for commercialization almost all exhibit low Na-ion conductivities of around 10^(-5)S cm^(-1)or lower.Here,we report a chloride solid electrolyte,Na_(2.7)ZFCl_(5.3)O_(0.7),which reaches a Na-ion conductivity of 2.29×10^(-4)S cm^(-1)at 25℃without involving overly expensive raw materials such as rare-earth chlorides or Na_(2)S.In addition to the efficient ion transport,Na_(2.7)ZrCl_(5.3)O_(0.7)also shows an excellent deformability surpassing that of the widely studied Na_(3)PS_(4),Na_(3)SbS_(4),and Na_(2)ZrCl_(6)solid electrolytes.The combination of these advantages allows the all-solid-state cell based on Na_(2.7)ZrCl_(5.3)O_(0.7)and NaCrO_(2)to realize stable room-temperature cycling at a much higher specific current than those based on other non-viscoelastic chloride solid electrolytes in literature(120 mA g^(-1)vs.12-55 mA g^(-1));after 100 cycles at such a high rate,the Na_(2.7)ZFCl_(5.3)O_(0.7)-based cell can still deliver a discharge capacity of 80 mAh g^(-1)at25℃.

Bunch-length measurement at a bunch-by-bunch rate based on time–frequency-domain joint analysis techniques and its application

This paper presents a new technique for measuring the bunch length of a high-energy electron beam at a bunch-by-bunch rate in storage rings.This technique uses the time–frequency-domain joint analysis of the bunch signal to obtain bunch-by-bunch and turn-by-turn longitudinal parameters,such as bunch length and synchronous phase.The bunch signal is obtained using a button electrode with a bandwidth of several gigahertz.The data acquisition device was a high-speed digital oscilloscope with a sampling rate of more than 10 GS/s,and the single-shot sampling data buffer covered thousands of turns.The bunch-length and synchronous phase information were extracted via offline calculations using Python scripts.The calibration coefficient of the system was determined using a commercial streak camera.Moreover,this technique was tested on two different storage rings and successfully captured various longitudinal transient processes during the harmonic cavity debugging process at the Shanghai Synchrotron Radiation Facility(SSRF),and longitudinal instabilities were observed during the single-bunch accumulation process at Hefei Light Source(HLS).For Gaussian-distribution bunches,the uncertainty of the bunch phase obtained using this technique was better than 0.2 ps,and the bunch-length uncertainty was better than 1 ps.The dynamic range exceeded 10 ms.This technology is a powerful and versatile beam diagnostic tool that can be conveniently deployed in high-energy electron storage rings.

Opportunities of Advanced Physical Studies at the Hefei Advanced Light Facility

Synchrotron radiation has transformed the role of xrays as a mainstream tool for probing the atomic and electronic structure of materials.Synchrotron-based xray sciences have been widely used to study the microscopic structure,electronic states,chemical composition.

Manipulating photogenerated electron flow in nickel single‐atom catalysts for photocatalytic CO_(2)reduction into tunable syngas

The key to designing photocatalysts is to orient the migration of photogenerated electrons to the target active sites rather than dissipate at inert sites.Herein,we demonstrate that the doping of phosphorus(P)significantly enriches photogenerated electrons at Ni active sites and enhances the performance for CO_(2)reduction into syngas.During photocatalytic CO_(2)reduction,Ni single‐atom‐anchored P‐modulated carbon nitride showed an impressive syngas yield rate of 85μmol gcat^(−1)h^(−1)and continuously adjustable CO/H_(2)ratios ranging from 5:1 to 1:2,which exceeded those of most of the reported carbon nitride‐based single‐atom catalysts.Mechanistic studies reveal that P doping improves the conductivity of catalysts,which promotes photogenerated electron transfer to the Ni active sites rather than dissipate randomly at low‐activity nonmetallic sites,facilitating the CO_(2)‐to‐syngas photoreduction process.

Healing the structural defects of spinel MnFe_(2)O_(4) to enhance the electrocatalytic activity for oxygen reduction reaction

Spinel metal oxides containing Mn,Co,or Fe(AB_(2)O_(4),A/B=Mn/Fe/Co)are one of the most promising nonPt electrocatalysts for oxygen reduction reaction(ORR)in alkaline conditions.However,the low conductivity of metal oxides and the poor intrinsic activities of transition metal sites lead to unsatisfactory ORR performance.In this study,eutectic molten salt(EMS)treatment is employed to reconstruct the atomic arrangement of MnFe_(2)O_(4)electrocatalyst as a prototype for enhancing ORR performance.Comprehensive analyses by using XAFS,soft XAS,XPS,and electrochemical methods reveal that the EMS treatment reduces the oxygen vacancies and spinel inverse in MnFe_(2)O_(4)effectively,which improves the electric conductivity and increases the population of more catalytically active Mn^(2+)sites with tetrahedral coordination.Moreover,the enhanced Mn-O interaction after EMS treatment is conducive to the adsorption and activation of O_(2),which promotes the first electron transfer step(generally considered as the ratedetermining step)of the ORR process.As a result,the EMS treated MnFe_(2)O_(4)catalyst delivers a positive shift of 40 mV in the ORR half-wave potential and a two-fold enhanced mass/specific activity.This work provides a convenient approach to manipulate the atomic architecture and local electronic structure of spinel oxides as ORR electrocatalysts and a comprehensive understanding of the structureperformance relationship from the molecular/atomic scale.

Surface-sensitive electronic structure of kagome superconductor CsV_(3)Sb_(5)

We systematically study the electronic structure of a kagome superconductor CsV_(3)Sb_(5)at different temperatures coveringboth its charge density wave state and normal state with angle-resolved photoemission spectroscopy.We observe thatthe V-shaped band aroundГshows three different behaviors,referred to as a/a',βandγ,mainly at different temperatures.Detailed investigations confirm that these bands are all from the same bulk Sb-p_(z)origin,but they are quite sensitiveto the sample surface conditions mainly modulated by temperature.Thus,the intriguing temperature dependent electronicbehavior of the band nearГis affected by the sample surface condition,rather than intrinsic electronic behavior originatingfrom the phase transition.Our result systematically reveals the confusing electronic structure behavior of the energy bandsaroundГ,facilitating further exploration of the novel properties in this material.

Cobalt phthalocyanine promoted copper catalysts toward enhanced electro reduction of CO_(2)to C_(2):Synergistic catalysis or tandem catalysis?

The activity and selectivity of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to C_(2)products on metal catalysts can be regulated by molecular surfactants.However,the mechanism behind it remains elusive and debatable.Herein,copper nanowires(Cu NWs)were fabricated and decorated with cobalt phthalocyanine(CoPc).The electronic interaction between the Cu NWs,CoPc,CO_(2) and CO_(2)RR intermediates were explored by density functional theory(DFT)calculations.It was found that the selectivity and activity of CO_(2)RR towards C_(2)products on Cu NWs were considerably enhanced from 35.2%to 69.9%by surface decoration of CoPc.DFT calculations revealed that CO_(2)RR can proceed in the interphase between Cu substrate and CoPc,and the CO_(2)RR intermediates could synergistically bond with both Cu and Co metal centre in CuNWs-CoPc,which favours the adsorption of CO_(2),CO and CO_(2)RR intermediates,thus reducing the free energy for CO-COcoupling towards C_(2)products.The synergistic interaction was further extended to phthalocyanine(Pc)and other metal phthalocyanine derivatives(MPc),where a relatively weaker synergistic interaction of COintermediates with MPc and Cu substrate and only a slight enhancement of CO_(2)RR towards C_(2) products were observed.This study demonstrates a synergistic catalysis pathway for CO_(2)RR,a novel perspective in interpreting the role of CoPc in enhancing the activity and selectivity of CO_(2)RR on Cu NWs,in contrast to the conventional tandem catalysis mechanism.