B18-Core EXAFS
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Charlie A. F.
Nason
,
Ajay Piriya
Vijaya Kumar Saroja
,
Wanjun
Ren
,
Yingkangzi
Mei
,
Asma
Sarguroh
,
Yupei
Han
,
Yi
Lu
,
Jamie A.
Gould
,
Tim I.
Hyde
,
Veronica
Celorrio
,
Gopinathan
Sankar
,
Yang
Xu
Diamond Proposal Number(s):
[39009, 39790]
Open Access
Abstract: The ultimate goal of potassium-ion batteries (KIBs) is to become a serious competitor to lithium-ion batteries (LIBs). Achieving this requires the development of high energy density negative electrode materials, with transition metal oxides emerging as the most promising candidates. However, despite their high theoretical capacities, most transition metal oxides still struggle to achieve high performance, often necessitating substantial nanostructuring. Ion-exchange presents a facile and effective process for enhancing material properties, yet the demonstration of the exchanged ions undergoing redox activity has not been previously reported for KIBs. Herein, this work reports Ni0.25K0.5TiNbO5, synthesized through the ion-exchange between K+ and Ni2+, as a novel negative electrode material for KIBs. The ion-exchanged material achieves a specific capacity of 304 mAh g−1 in the first cycle and 162 mAh g−1 after 10 cycles, corresponding to a 240% and 156% increase compared to the pristine, unexchanged KTiNbO5 at the same cycle numbers. The structure–performance relationship was investigated in detail, shedding light on the previously unknown relationships between the level of hydration, degree of exchange and the performance of ion-exchanged materials. Furthermore, the exchanged Ni was demonstrated to be reversibly redox active, contributing to the observed capacity and representing a first for ion-exchanged materials in the KIB literature.
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Sep 2025
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I20-Scanning-X-ray spectroscopy (XAS/XES)
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Diamond Proposal Number(s):
[26014]
Open Access
Abstract: We successfully synthesised ceria and Cu-doped ceria thin films on fluorine-doped tin oxide (FTO) glass using electrochemical deposition methods. Although X-ray diffraction characterisation did not confirm the presence of pure CeO2 phase, XPS and high-resolution fluorescence detection method to collect XANES data at Ce L3 edge confirmed the presence of only Ce4+ and the spectral features resembled that of CeO2 in all the as-synthesised samples. In situ reactivity studies in the H2 atmosphere of these samples employing XANES data, recorded during the heating and cooling cycle, revealed the extent of Ce4+ conversion to Ce3+. Most importantly the stability of converted Ce3+ appears to depend on the presence of reducible transition metal, where the presence of copper ions indeed decreased the reduction temperature of Ce4+ and upon cooling the formed Ce3+ appears to be stable in a reducing atmosphere. In the absence of copper, not only is the extent of reduction to Ce3+ much less compared with the copper-containing samples but also, the reduced Ce3+ ions appear to reoxidise to Ce4+ upon cooling to room temperature. These results are in line with observed results of powder CeO2 samples typically used as catalyst supports.
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May 2025
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B18-Core EXAFS
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Benjamin
Moss
,
Katrine L.
Svane
,
David
Nieto-Castro
,
Reshma R.
Rao
,
Soren B.
Scott
,
Cindy
Tseng
,
Michael
Sachs
,
Anuj
Pennathur
,
Caiwu
Liang
,
Louise I.
Oldham
,
Eva
Mazzolini
,
Lole
Jurado
,
Gopinathan
Sankar
,
Stephen
Parry
,
Veronica
Celorrio
,
Jahan M.
Dawlaty
,
Jan
Rossmeisl
,
Jose Ramon
Galán-Mascarós
,
Ifan E. L.
Stephens
,
James R.
Durrant
Diamond Proposal Number(s):
[30663]
Open Access
Abstract: A barrier to understanding the factors driving catalysis in the oxygen evolution reaction (OER) is understanding multiple overlapping redox transitions in the OER catalysts. The complexity of these transitions obscure the relationship between the coverage of adsorbates and OER kinetics, leading to an experimental challenge in measuring activity descriptors, such as binding energies, as well as adsorbate interactions, which may destabilize intermediates and modulate their binding energies. Herein, we utilize a newly designed optical spectroelectrochemistry system to measure these phenomena in order to contrast the behavior of two electrocatalysts, cobalt oxyhydroxide (CoOOH) and cobalt–iron hexacyanoferrate (cobalt–iron Prussian blue, CoFe-PB). Three distinct optical spectra are observed in each catalyst, corresponding to three separate redox transitions, the last of which we show to be active for the OER using time-resolved spectroscopy and electrochemical mass spectroscopy. By combining predictions from density functional theory with parameters obtained from electroadsorption isotherms, we demonstrate that a destabilization of catalytic intermediates occurs with increasing coverage. In CoOOH, a strong (∼0.34 eV/monolayer) destabilization of a strongly bound catalytic intermediate is observed, leading to a potential offset between the accumulation of the intermediate and measurable O2 evolution. We contrast these data to CoFe-PB, where catalytic intermediate generation and O2 evolution onset coincide due to weaker binding and destabilization (∼0.19 eV/monolayer). By considering a correlation between activation energy and binding strength, we suggest that such adsorbate driven destabilization may account for a significant fraction of the observed OER catalytic activity in both materials. Finally, we disentangle the effects of adsorbate interactions on state coverages and kinetics to show how adsorbate interactions determine the observed Tafel slopes. Crucially, the case of CoFe-PB shows that, even where interactions are weaker, adsorption remains non-Nernstian, which strongly influences the observed Tafel slope.
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Mar 2024
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B07-B1-Versatile Soft X-ray beamline: High Throughput ES1
B18-Core EXAFS
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Diamond Proposal Number(s):
[29781, 29392]
Open Access
Abstract: Fe-based potassium Prussian blue analogs (K-PBAs) are commonly used as K-ion battery (KIB) cathodes. Interestingly, K-PBAs are appealing cathodes for Na-ion batteries (NIBs). In a hybrid NIB cell, where Na-ion is in the electrolyte and K-ion is in the PBA cathode, cation intercalation and electrochemical performance of the cathode can be significantly affected by [Fe(CN)6]4− anion vacancy. This work studies the effect of anion vacancy in K-PBAs on regulating K-ion/Na-ion intercalation mechanism in hybrid NIB cells, by comparing two K-PBA cathodes with different vacancy contents. The results demonstrate that introducing a level of anion vacancy can maximize the number of K-ion intercalation sites and enhance K-ion diffusion in the PBA framework. This facilitates K-ion intercalation and suppresses Na-ion intercalation, resulting in a K-ion-dominated and high-discharge-voltage ion storage process in the hybrid NIB cell. The K-PBA cathode with 20% anion vacancy delivers 128 mAh g−1 at 25 mA g−1 and 67 mAh g−1 at 1000 mA g−1, as well as retains 89% and 81% capacity after 100 and 300 cycles, respectively. It completely outperforms the counterpart with 7% anion vacancy, which exhibits increased Na-ion intercalation but overall deteriorated ion storage.
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Sep 2023
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B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS
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Open Access
Abstract: Understanding how the microstructure of the active Cu0 component in the commercially applicable Cu/ZnO/Al2O3(−Cs2O) low-temperature water-gas shift catalyst evolves under various H2 partial pressures in the presence/absence of a Cs promoter during thermal activation has been investigated. Time-resolved XRD and spatially-resolved XRD-CT data were measured as a function of H2 concentration along a packed bed reactor to elucidate the importance of the zincite support and the effect of the promoter on Cu sintering mechanisms, dislocation character and stacking fault probability. The rate of Cu reduction showed a dependency on [Cs], [H2] and bed height; lower [Cs] and higher [H2] led to a greater rate of metallic copper nanoparticle formation. A deeper analysis of the XRD line profiles allowed for determining a greater edge character to the dislocations and subsequent stacking fault probability was also observed to depend on higher [H2], smaller Cu0 (and ZnO) crystallite sizes, increased [ZnO] (30 wt.%, sCZA) and lower temperature. The intrinsic activity of Cu/ZnO/Al2O3 methanol synthesis catalysts has been intimately linked to the anisotropic behaviour of copper, and thus the presence of lattice defects; to the best knowledge of the authors, this study is the first instance in which this type of analysis has been applied to LT-WGS catalysts.
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Aug 2022
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B18-Core EXAFS
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Diamond Proposal Number(s):
[6966]
Open Access
Abstract: Use of in situ combined X-ray diffraction and X-ray absorption spectroscopy for the study of the thermal decomposition of zinc peroxide to zinc oxide is reported here. Comparison of data extracted from both X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) with thermo gravimetric analysis (TGA) enabled us to follow the nature of the conversion of ZnO2 to ZnO. A temperature range between 230 and 350oC appears to show a very poorly crystalline ZnO is formed prior to the formation of ordered ZnO material. Both the decrease in white line intensity in the Zn K-edge XANES and resulting lower coordination numbers estimated from analysis of Zn K-edge data of ZnO heated at 500oC, in comparison to bulk ZnO, suggest that that the ZnO produced by this method has significant defects in the system.
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Apr 2021
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I20-Scanning-X-ray spectroscopy (XAS/XES)
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Diamond Proposal Number(s):
[18039]
Open Access
Abstract: Copper containing oxides are widely used in a range of catalytic applications. Here, we report the use of Cu K-edge high resolution XANES to determine the local site symmetry of copper ions during the thermal treatment of a Cu-Cr-Fe oxide catalyst. We exploited the Cu K-edge XANES spectral features, in particular the correlation between area under the pre-edge peak and its position to determine the local environment of Cu2+ ions. The information gained from this investigation rules out the presence of Cu2+ ions in a tetrahedral, square planar geometry, a mixture of these sites or in a reduced oxidation state. Evidence is presented that the Cu2+ ions in the Cu-Cr-Fe oxide system are present in a distorted octahedral environment.
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Feb 2021
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B18-Core EXAFS
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B.
Venezia
,
E.
Cao
,
Santhosh K.
Matam
,
C.
Waldron
,
G.
Cibin
,
E. K.
Gibson
,
S.
Golunski
,
P. P.
Wells
,
I.
Silverwood
,
C. R. A.
Catlow
,
G.
Sankar
,
A.
Gavriilidis
Diamond Proposal Number(s):
[19359]
Open Access
Abstract: Operando X-ray absorption spectroscopy (XAS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and mass spectrometry (MS) provide complementary information on the catalyst structure, surface reaction mechanisms and activity relationships. The powerful combination of the techniques has been the driving force to design and engineer suitable spectroscopic operando reactors that can mitigate limitations inherent to conventional reaction cells and facilitate experiments under kinetic regimes. Microreactors have recently emerged as effective spectroscopic operando cells due to their plug-flow type operation with no dead volume and negligible mass and heat transfer resistances. Here we present a novel microfabricated reactor that can be used for both operando XAS and DRIFTS studies. The reactor has a glass–silicon–glass sandwich-like structure with a reaction channel (3000 μm × 600 μm; width × depth) packed with a catalyst bed (ca. 25 mg) and placed sideways to the X-ray beam, while the infrared beam illuminates the catalyst bed from the top. The outlet of the reactor is connected to MS for continuous monitoring of the reactor effluent. The feasibility of the microreactor is demonstrated by conducting two reactions: i) combustion of methane over 2 wt% Pd/Al2O3 studied by operando XAS at the Pd K-edge and ii) CO oxidation over 1 wt% Pt/Al2O3 catalyst studied by operando DRIFTS. The former shows that palladium is in an oxidised state at all studied temperatures, 250, 300, 350, 400 °C and the latter shows the presence of linearly adsorbed CO on the platinum surface. Furthermore, temperature-resolved reduction of palladium catalyst with methane and CO oxidation over platinum catalyst are also studied. Based on these results, the catalyst structure and surface reaction dynamics are discussed, which demonstrate not only the applicability and versatility of the microreactor for combined operando XAS and DRIFTS studies, but also illustrate the unique advantages of the microreactor for high space velocity and transient response experiments.
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Oct 2020
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I20-Scanning-X-ray spectroscopy (XAS/XES)
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Diamond Proposal Number(s):
[18039]
Abstract: Cu2O is an attractive photocathode for important renewable energy reactions such as water splitting and CO2 reduction. Electrodeposition is commonly used to deposit Cu2O films on conductive substrates due to its simplicity and consistency. However, structural descriptors, linking electrodeposition parameters, film structure and the catalytic properties are elusive. A variety of Cu2O films reported by many research groups would often display vastly different electronic properties and catalytic activity, while appear indistinguishable under common characterisation tools. In this work, we take a systematic look into electrochemically deposited Cu2O and investigate the impact of deposition parameters towards the bulk and surface chemistry of the deposited film. Specifically, we employ high resolution XANES for thorough quantitative analysis of the Cu2O films, alongside more common characterisation methods like XRD, SEM and Raman spectroscopy. Photoelectrochemical (PEC) studies reveal an unexpected trend, where the highest PEC activity appears to correlate with the amount of Cu2+ content. Other factors which also affect the PEC activity and stability are film thickness and crystallite grain size. Our study shows that the use of high resolution XANES, though not perfect due to possible self-absorption issue, is apt for extracting compositional descriptor in concentrated thin film samples from the pre-edge energy position analysis. This descriptor can serve as a guide for future development of more active Cu2O based films for wide range of PEC processes as well as for solar cell applications.
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Sep 2020
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Zilu
Liu
,
Tianjun
Liu
,
Christopher N.
Savory
,
José P.
Jurado
,
Juan Sebastián
Reparaz
,
Jianwei
Li
,
Long
Pan
,
Charl F. J.
Faul
,
Ivan P.
Parkin
,
Gopinathan
Sankar
,
Satoru
Matsuishi
,
Mariano
Campoy‐quiles
,
David O.
Scanlon
,
Martijn A.
Zwijnenburg
,
Oliver
Fenwick
,
Bob C.
Schroeder
Open Access
Abstract: Organometallic coordination polymers (OMCPs) are a promising class of thermoelectric materials with high electrical conductivities and thermal resistivities. The design criteria for these materials, however, remain elusive and so far material modifications have been focused primarily on the nature of the metal cation to tune the thermoelectric properties. Herein, an alternative approach is described by synthesizing new organic ligands for OMCPs, allowing modulation of the thermoelectric properties of the novel OMCP materials over several orders of magnitude, as well as controlling the polarity of the Seebeck coefficient. Extensive material purification combined with spectroscopy experiments and calculations furthermore reveal the charge‐neutral character of the polymer backbones. In the absence of counter‐cations, the OMCP backbones are composed of air‐stable, ligand‐centered radicals. The findings open up new synthetic possibilities for OMCPs by removing structural constraints and putting significant emphasis on the molecular structure of the organic ligands in OMCP materials to tune their thermoelectric properties.
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Jun 2020
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