Recent XAFS development and its
application in Shanghai Synchrotron
Radiation Facility
Zheng Jiang
Shanghai Synchrotron Radiation Facility (SSRF)
Shanghai Advanced Research Institute, CAS
Shanghai Institute of Applied Physics, CAS
Sept 20, 2022

Zhangjiang Comprehensive National Science Center
SSRF Phase II

10 MW SULF
NCPSS

SXFEL
SBP

SSRF Phase I

5 MW SULF

SHINE
We will actively participate in the construction of Zhangjiang comprehensive
National Science Center, join the international club.

Outline◼ X-ray Spectroscopy Platforms in SSRF
➢ BL14W1-XAFS beamline➢ D-line/E-line/RMB/Hard X-ray Spectroscopy beamline◼ X-ray Spectroscopy Platforms in SHINE◼ Application of X-ray Spectroscopy in Catalysis

SSRF Beamlines layout

X-ray Spectroscopy Platforms at SSRF

BL14W1-XAFS

Hard X-ray Spectroscopy

Dynamic D-line

Energy Material E-line Radioactive Materials
Beamline

QXAFS

DXAFS+IR

APPES/STM/XES/XRS…. XES/micro-spectroscopy

原位XAFS

2005

2009

2016

2018

2020

2022
Timeline ofconstruction

Spectroscopy Methods in BL14W1
High energy resolution spectroscopy

TRXEOLQXAFS

Single/multiple-crystal Johann spectrometer

TRXEOL system

QXAFS result

High pressure XAFSIn situ/operando XAFS

K-B/capillary isoelectric focusing

High-temperature/low-temperature cells

Users’ Research Achievement of BL14W1

Chemistry (catalysis) has always been the field with the largest demandand highest quality output.

Hard X-ray Spectroscopy Beamline
Main Techniques:• Transmission XAFS
• Fluorescence XAFS
• Quick Scanning XAFS• Combined XAFS and XRD• Operando XAFS

Industrial-relevant high current density
OERHERFe‒(OH)4‒Ni4OH

Ni4Mo

Hard X-ray Spectroscopy Beamline
Energy range

5~30 keV

Spot size

500×500 m2Photon flux

4×1011phs/s@10 keV, Si(111)Energy resolution

2×10-4@10keV, Si(111)
5×10-5@10keV, Si(311)Time resolution~100 ms

Operando XAS revealed theintrinsic hydrogen evolution
reaction (HER) mechanism of Nibased catalyst with surface
modification of Fe.
Energy Environ. Sci. 2021, 14,4610-4619

Design and Layout of D-line
ED-XAS & IR
Energy range

5~25 keV; 100~1000 cm-1

Spot size

20×20 m2; 100×100 m2@1000 cm-1

Photon flux

3.8×1012phs/s·300eV BW@7keV;
1013phs/s·0.1%BW@4200 cm

Energy resolution

2×10-4@Cu K-edge; 16cm-1Time resolution~10 ms(FTIR), ~60 s(ED-XAS)

In situ cell temperature

RT~600KBM
IR station
IR station(10~10000 cm-1)⚫IR Spectroscopy⚫ IR Microspectroscpy⚫Nano- FTIRED-XAS station(5~25keV)⚫Time resolved ED-XAS (～60s)⚫Pump-probe ED-XAS （～100ps）⚫Extreme condition ED-XAS（<20Gpa, ～3000K, ～20T…)

ED-XAS station

IVU
IR & ED-XAS station
IR & ED-XAS station (10~10000 cm-1,5~25keV)⚫Time-resolved IR+ ED-XAS（~ms）

Science Object of E-line
Focusing on surface interface chemistry, electrochemistry, self-assembly,and photoelectric conversion, etc.

Electronic structure•Occupied state•Unoccupied state

Spatial dimention•Surface and interface•BulkOperando measurement•Temperature and pressure•Electronic/magnetic field• Measurement methods:
XAS, XES, XRS, APPES, RXES, REXS

•Understanding the reaction mehanism•Regulating the reaction performanceDesign and Layout of E-line

hv: 2.3 keV-18 keVEnergy resolution: 4eV@ 6keV
HERFD-XAFS

hv: 130eV -10 keV

hv: 130eV -2 keVEnergy resolution: 4000@ 445eV RIXS

Radioactive Materials Beamline (RMB)
HRXPD station(5~50 keV)
⚫ XRD, GIXRD⚫ High Resolution X-ray Powder
Diffraction（HRXPD）
Ventilation

Micro-beam station(5~35keV)⚫ μ-XAFS,⚫ μ-XRD⚫ μ-XRFsystemCabinet for interim
sample storage

HRXPD station

X-ray
Micro-beam station
XAS & HR-XAS/XES station

XAS & HR-XAS/XES station (3~50 keV)
⚫ XAS
⚫ HR-XAS⚫ XES
Tungsten shielding of sample

Outline◼ X-ray Spectroscopy Platforms in SSRF
➢ BL14W1-XAFS beamline➢ D-line/E-line/RMB/Hard X-ray Spectroscopy beamline◼ X-ray Spectroscopy Platforms in SHINE◼ Application of X-ray Spectroscopy in Catalysis

10 End-Stations @ SHINE Facility
FEL-I Hard X-ray End-stations• HSS: Hard X-ray Scattering and Spectroscopy• CDS: Coherent Diffraction Endstation for Single Molecules and Particles• SEL: Station of Extreme Light➢ XFEL + 100 PW Laser System

FEL-II Soft X-ray End-stations• AMO: Atomic, Molecular, and Optical Science• SES: Spectrometer for Electronic Structure• SSS: Soft X-ray Scattering and Spectroscopy

FEL-III Hard X-ray End-stations••••

HXS: Hard X-ray Spectroscopy
SFX: Serial Femtosecond Crystallography
CDE: Coherent Diffraction Imaging
HED: High Energy Density ScienceTsu-Chien Weng

Hard X-ray Scattering & Spectroscopy Endstation
Measuring the element excitation in quantum associated materials in thecase of energy, momentum and time.
◼ RIXS◼ HERFD-XAS
Energy range: 3-15 keVRev. Mod. Phys. 83, 705 (2011)

Kaiyu Zhang Jianwei Meng

Hard X-ray Spectroscopy Endstation
LayoutParameters
Xing Liu Ruixue Zhu

Peng LiuOutline◼ X-ray Spectroscopy Platforms in SSRF
➢ BL14W1-XAFS beamline➢ D-line/E-line/RMB/Hard X-ray Spectroscopy beamline◼ X-ray Spectroscopy Platforms in SHINE◼ Application of X-ray Spectroscopy in Catalysis

F-T Process

IndirectConversion

CarbonConversion

Toward Great Strategy Demand
Ultimate goalDirectConversion

Emission

Hydrogen Energy
Development

H2
Water Electrolysis
Water Photolysis
Fuel Cells

Eliminate

Li-ion Battery

Difference spectra —— surface informationDifference technique （）Intermediate

Before reaction

Difference

Surface sensitive
Shortage：weak intensity

Phys. Chem. Chem. Phys., 2010, 12, 5514–5534

In Situ Spectroscopy Reveals Proton Transfer in EDL
 Thermocatalysis:⚫ Solid-Gas interface

ETEMSTM
Building a catalytic reaction modelDFT Electrocatalysis：⚫ Solid-Liquid interface

EDL

Solvent effect at the solid-liquid interface

HER @ Sub-Nanometric PlatinumCharacterization

PtOx



Performance >commercial Pt/C
Hao Zhang
0.5 M
H2SO4

 Only 18 mV overpotential at 10 mA/cm2(23mV for commercial Pt/C) high mass activity (19 A/mg Pt vs 1.7 A/mg

Pt of Pt/C at an overpotential of 50 mV)ACS Appl. Mater. Interfaces 2021, 13, 47252−47261

Operando XAFS Reveals Structural Evolution

PtOx

HERRe-oxidation

Pt clusters

PtOx

 In high potential region, the white-line intensity decreasing→Pt-C/O bond breaking
 In low potential region, the white-line intensity increasing→increase in hydrogen coverage on thePt surface

Structure-performance Relationship

The simultaneous increases in Pt−O (L) radial distance and hydrogen coverage at
the SNM-Pt/electrolyte interface are closely correlated, which implies that more
flexible interfacial water more efficiently transfers the proton through the EDLinterface and leads to a faster reaction rate for HER.

XANES —— spatial configuration

CO2 Reduction Reaction (CO2RR)
Peaking carbon dioxide emissions before 2030
Achieving carbon neutrality before 2060

J. Mater. Chem. A, DOI: 10.1039/D0TA03525D

Synthesis of Ni SAC based on ZIF-8

Ni-N3C

Ni-N2V2
Although the same synthesis method was performed, different atomic structures
was obtained. The coordination environment of ZIF-8 Ni SACs has not been
determined.

CO2RR based on Ni SACab

Potential-dependent
Volcanic Selectivity
1 mc

5 nm
NiCNO100 nm

The production of CO became predominant in the range of −0.5 to −0.9 V. The

highest CO Faradaic efficiency of 99% was achieved at a potential of −0.67 V.
ACS Catal. 2022, 12, 14, 8676–8686

Spectroscopy methods uncover the atomic structure

The Ni species are atomicallydispersed and mainly bonds withpyrrole-type N species.

XANES simulation determines fineconfiguration

Disordered pyrroletype Ni-N4O2 with

the Ni center out of
the N4 planeOperando XAFS analysis

The applied potential induced local structurechanges.

XANES simulation

The change of the structure of the active site regulates the electronic state andthus affects potential-dependent volcanic selectivity changes.

High energy resolution of XES

High energy-resolution XES

The resolution of X-ray spectroscopy is related to the life
broaden of the final state.
Heisenberg uncertainty∆𝐸 = ℏ/𝑡High Energy Resolution X-ray Spectroscopy

Bingbao Mei

Von Hamos spectrometerOperando XES analysis of Cu2O/Cu film

It is challenging to gain further information
about the structure and chemical state ofthese thick samples based only on XAFS
due to the strong self-absorption affect.
Bingbao Mei, Zheng Jiang*, et al. X-Ray Spectrometry. 2019, 49, 251–259

CuPc model catalyst for CO2RR➢ Defined atomic configuration of CuN4C8➢ Guiding the study of SACs

Journal of Energy Chemistry, 64 (2022) 1–7

◼ Operando XES identified the structural evolution

Gradual strengthen of contour center at 8980 eV as thepotential increases indicates the formation of a novel structure.

◼ Peak fitting and LCF determined the component changes
LCFThe applied potential directly induced thestructural transformation of Cu(II) to Cu(0)◼ HERFD-XANES  analysis
Cu(0)Cu(II)

 = (CO2 , potential) −  (dry)◼ HERFD-XANES simulation based on Cu clusters offer active sites for C-C couplingAcknowledgement
BSRF, NSRL, SSRF, SHINE & Beamline scientists: Tsu-Chien Weng, Fei
Song, Xiangjun Wei, Jiong Li, Fenggang Bian, Yanqing Wu.