B16-Test Beamline
E01-JEM ARM 200CF
I12-JEEP: Joint Engineering, Environmental and Processing
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Zifan
Wang
,
Jingwei
Chen
,
Radim
Kocich
,
Samuel
Tardif
,
Igor P.
Dolbnya
,
Lenka
Kunčická
,
Jean-Sébastien
Micha
,
Konstantinos
Liogas
,
Oxana
Magdysyuk
,
Ivo
Szurman
,
Alexander M.
Korsunsky
Diamond Proposal Number(s):
[25467, 28397, 28418]
Open Access
Abstract: To explore an effective route of customizing the superelasticity (SE) of NiTi shape memory alloys via modifying the grain structure, binary Ni55Ti45 (wt) alloys were fabricated in as-cast, hot swaged, and hot-rolled conditions, presenting contrasting grain sizes and grain boundary types. In situ synchrotron X-ray Laue microdiffraction and in situ synchrotron X-ray powder diffraction techniques were employed to unravel the underlying grain structure mechanisms that cause the diversity of SE performance among the three materials. The evolution of lattice rotation, strain field, and phase transformation has been revealed at the micro- and mesoscale, and the effect of grain structure on SE performance has been quantified. It was found that (i) the Ni4Ti3 and NiTi2 precipitates are similar among the three materials in terms of morphology, size, and orientation distribution; (ii) phase transformation happens preferentially near high-angle grain boundary (HAGB) yet randomly in low-angle grain boundary (LAGB) structures; (iii) the smaller the grain size, the higher the phase transformation nucleation kinetics, and the lower the propagation kinetics; (iv) stress concentration happens near HAGBs, while no obvious stress concentration can be observed in the LAGB grain structure during loading; (v) the statistical distribution of strain in the three materials becomes asymmetric during loading; (vi) three grain lattice rotation modes are identified and termed for the first time, namely, multi-extension rotation, rigid rotation, and nondispersive rotation; and (vii) the texture evolution of B2 austenite and B19′ martensite is not strongly dependent on the grain structure.
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Jun 2022
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[28223]
Open Access
Abstract: The metal-organic framework MOF-808 contains Zr6O8 nodes with a high density of vacancy sites, which can incorporate carboxylate-containing functional groups to tune chemical reactivity. Although the postsynthetic methods to modify the chemistry of the Zr6O8 nodes in MOFs are well known, tackling these alterations from a structural perspective is still a challenge. We have combined infrared spectroscopy experiments and first-principles calculations to identify the presence of node vacancies accessible for chemical modifications within the MOF-808. We demonstrate the potential of our approach to assess the decoration of MOF-808 nodes with different catechol–benzoate ligands. Furthermore, we have applied advanced synchrotron characterization tools, such as pair distribution function analyses and X-ray absorption spectroscopy, to resolve the atomic structure of single metal sites incorporated into the catechol groups postsynthetically. Finally, we demonstrate the catalytic activity of these MOF-808 materials decorated with single copper sites for 1,3-dipolar cycloadditions.
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May 2022
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I22-Small angle scattering & Diffraction
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Arindam
Pramanik
,
Zexi
Xu
,
Shazana H.
Shamsuddin
,
Yazan S.
Khaled
,
Nicola
Ingram
,
Thomas
Maisey
,
Darren
Tomlinson
,
P. Louise
Coletta
,
David
Jayne
,
Thomas A.
Hughes
,
Arwen
Tyler
,
Paul A.
Millner
Diamond Proposal Number(s):
[16566, 26258, 28627]
Abstract: Nanomedicines, while having been approved for cancer therapy, present many challenges such as low stability, rapid clearance, and nonspecificity leading to off-target toxicity. Cubosomes are porous lyotropic liquid crystalline nanoparticles that have shown great premise as drug delivery vehicles; however, their behavior in vivo is largely underexplored, hindering clinical translation. Here, we have engineered cubosomes based on the space group Im3m that are loaded with copper acetylacetonate as a model drug, and their surfaces are functionalized for the first time with Affimer proteins via copper-free click chemistry to actively target overexpressed carcinoembryonic antigens on LS174T colorectal cancer cells. Unlike nontargeted cubosomes, Affimer tagged cubosomes showed preferential accumulation in cancer cells compared to normal cells not only in vitro (2D monolayer cell culture and 3D spheroid models) but also in vivo in colorectal cancer mouse xenografts, while exhibiting low nonspecific absorption and toxicity in other vital organs. Cancerous spheroids had maximum cell death compared to noncancerous cells upon targeted delivery. Xenografts subjected to targeted drug-loaded cubosomes showed a 5–7-fold higher drug accumulation in the tumor tissue compared to the liver, kidneys, and other vital organs, a significant decrease in tumor growth, and an increased survival rate compared to the nontargeted group. This work encompasses the first thorough preclinical investigation of Affimer targeted cubosomes as a cancer therapeutic.
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Feb 2022
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B18-Core EXAFS
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Diamond Proposal Number(s):
[21533]
Open Access
Abstract: The electrochemical conversion of carbon dioxide (CO2) to useful chemical fuels is a promising route toward the achievement of carbon neutral and carbon negative energy technologies. Copper (Cu)- and Cu oxide-derived surfaces are known to electrochemically convert CO2 to high-value and energy-dense products. However, the nature and stability of oxidized Cu species under reaction conditions are the subject of much debate in the literature. Herein, we present the synthesis and characterization of copper-titanate nanocatalysts, with discrete Cu–O coordination environments, for the electrochemical CO2 reduction reaction (CO2RR). We employ real-time in situ X-ray absorption spectroscopy (XAS) to monitor Cu species under neutral-pH CO2RR conditions. Combination of voltammetry and on-line electrochemical mass spectrometry with XAS results demonstrates that the titanate motif promotes the retention of oxidized Cu species under reducing conditions for extended periods, without itself possessing any CO2RR activity. Additionally, we demonstrate that the specific nature of the Cu–O environment and the size of the catalyst dictate the long-term stability of the oxidized Cu species and, subsequently, the product selectivity.
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Jan 2022
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B21-High Throughput SAXS
I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[17972, 16970]
Abstract: Catalytically active materials for the enhancement of personalized protective equipment (PPE) could be advantageous to help alleviate threats posed by neurotoxic organophosphorus compounds (OPs). Accordingly, a chimeric protein comprised of a supercharged green fluorescent protein (scGFP) and phosphotriesterase from Agrobacterium radiobacter (arPTE) was designed to drive the polymer surfactant (S–)-mediated self-assembly of microclusters to produce robust, enzymatically active materials. The chimera scGFP-arPTE was structurally characterized via circular dichroism spectroscopy and synchrotron radiation small-angle X-ray scattering, and its biophysical properties were determined. Significantly, the chimera exhibited greater thermal stability than the native constituent proteins, as well as a higher catalytic turnover number (kcat). Furthermore, scGFP-arPTE was electrostatically complexed with monomeric S–, driving self-assembly into [scGFP-arPTE][S–] nanoclusters, which could be dehydrated and cross-linked to yield enzymatically active [scGFP-arPTE][S–] porous films with a high-order structure. Moreover, these clusters could self-assemble within cotton fibers to generate active composite textiles without the need for the pretreatment of the fabrics. Significantly, the resulting materials maintained the biophysical activities of both constituent proteins and displayed recyclable and persistent activity against the nerve agent simulant paraoxon.
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Dec 2021
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B18-Core EXAFS
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Diamond Proposal Number(s):
[14239]
Abstract: Bulk isocubanite (CuFe2S3) was synthesized via a multistep high-temperature synthesis and was investigated as an anode material for sodium-ion batteries. CuFe2S3 exhibits an excellent electrochemical performance with a capacity retention of 422 mA h g–1 for more than 1000 cycles at a current rate of 0.5 A g–1 (0.85 C). The complex reaction mechanism of the first cycle was investigated via PXRD and X-ray absorption spectroscopy. At the early stages of Na uptake, CuFe2S3 is converted to form crystalline CuFeS2 and nanocrystalline NaFe1.5S2 simultaneously. By increasing the Na content, Cu+ is reduced to nanocrystalline Cu, followed by the reduction of Fe2+ to amorphous Fe0 while reflections of nanocrystalline Na2S appear. During charging up to −5 Na/f.u., the intermediate NaFe1.5S2 appears again, which transforms in the last step of charging to a new unknown phase. This unknown phase together with NaFe1.5S2 plays a key role in the mechanism for the following cycles, evidenced by the PXRD investigation of the second cycle. Even after 400 cycles, the occurrence of nanocrystalline phases made it possible to gain insights into the alteration of the mechanism, which shows that CuxS phases play an important role in the region of constant specific capacity.
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Nov 2021
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B18-Core EXAFS
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Diamond Proposal Number(s):
[20060]
Abstract: Electrochemical performance of the layered compound CrPS4 for the usage as anode material in sodium-ion batteries (SIBs) was examined and exceptional reversible long-term capacity and capacity retention were found. After 300 cycles, an extraordinary reversible capacity of 687 mAh g–1 at a current rate of 1 A g–1 was achieved, while rate capability tests showed an excellent capacity retention of 100%. Detailed evaluation of the data evidence a change of the electrochemical reaction upon cycling leading to the striking long-term performance. Further investigations targeted the reaction mechanism of the first cycle by applying complementary techniques, i.e., powder X-ray diffraction (XRD), pair distribution function (PDF) analysis, X-ray absorption spectroscopy (XAS), and 23Na/31P magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The results indicated an unexpectedly complex reaction pathway including formation of several intercalation compounds, depending on the amount of Na inserted at the early discharge states and subsequent conversion to Na2S and strongly disordered metallic Cr at the completely discharged state. While XAS measurements suggest no further presence of intermediates after formation of Na intercalation compounds, several different phases are detected via MAS NMR upon continued discharging. Especially the data obtained from the MAS NMR investigations therefore point toward a very complex reaction pathway. Furthermore, solid electrolyte interphase (SEI) formation, resulting in the presence of NaF, was observed. After recharging the anode material, no structural long-range order occurred, but short-range order indeed resembled the local environment of the starting material, to a certain extent.
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Nov 2021
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[22209]
Open Access
Abstract: The clathrate was prepared in a Sn flux using conditions that favor the type VIII over type I clathrate structure as described previously and the composition was confirmed by single-crystal X-ray diffraction (XRD). More details can be found in the Supporting Information. Slurries containing the active material (type VIII clathrate or commercially obtained β-Sn powder), carbon black, and binder were prepared and coated onto the copper foil (see the Supporting Information). These composite electrodes were then lithiated galvanostatically in half-cells with lithium metal and then extracted for ex situ measurements. Synchrotron X-ray pair distribution (PDF) measurements were conducted at Diamond Light Source (Didcot, U.K.) at the I15-I dedicated PDF beamline with λ = 0.161669 Å. The atomic PDF, G(r), as defined by Billinge et al., was generated from the total scattering data using PDFgetx3 within the xPDF suite software package. The first-principles density functional theory (DFT) calculations were performed in a similar manner to our previous work and are described in more detail in the Supporting Information. The Gibbs free-energy change, average lithiation voltage, and formation energy were calculated as described previously. The climbing image nudged elastic band (NEB) method was used to calculate the Li migration barriers.
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Sep 2021
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B18-Core EXAFS
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Abstract: Joule heating studies on nanoparticle/nanocarbon hybrid aerogels have been reported, but systematic investigations on hydrotalcite-derived catalysts supported onto reduced graphene oxide (rGO) aerogels are rare. In this study, hydrotalcite-derived Cu-Al2O3 nanoparticles were incorporated into a porous and multifunctional rGO aerogel support for fabricating electrically conducting Cu-Al2O3/rGO hybrid aerogels, and their properties were investigated in detail. The hybridization of Cu-Al2O3 with a 3D nanocarbon support network imparts additional functionalities to the widely used functional inorganic nanoparticles, such as direct electrical framework heating and easy regeneration and separation of spent nanoparticles, with well-spaced nanoparticle segregation. 3D variable-range hopping model fitting confirmed that electrons were able to reach the entire aerogel to enable uniform resistive heating. The conductivity of the nanocarbon support framework facilitates uniform and fast heating (up to 636 K/min) of the embedded nanoparticles at very low energy consumption, while the large porosity and high thermal conductivity enable efficient heat dissipation during natural cooling (up to 336 K/min). The thermal stability of the hybrid aerogel was demonstrated by repeated heating/cooling cycling at different temperatures that were relevant to important industrial applications. The facile synthetic approach can be easily adapted to fabricate other types of multifunctional nanoparticle/nanocarbon hybrid aerogels, such as the MgAl-MMO/rGO aerogel and the Ni-Al2O3/rGO aerogel. These findings open up new routes to the functionalization of inorganic nanoparticles and extend their application ranges that involve electrical/thermal heating, temperature-dependent catalysis, sorption, and sensing.
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Jul 2021
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I20-Scanning-X-ray spectroscopy (XAS/XES)
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Eko
Budiyanto
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Swen
Zerebecki
,
Claudia
Weidenthaler
,
Tim
Kox
,
Stephane
Kenmoe
,
Eckhard
Spohr
,
Serena
Debeer
,
Olaf
Rudiger
,
Sven
Reichenberger
,
Stephan
Barcikowski
,
Harun
Tuysuz
Diamond Proposal Number(s):
[25636]
Open Access
Abstract: Herein, we report nanosecond, single-pulse laser post-processing (PLPP) in a liquid flat jet with precise control of the applied laser intensity to tune structure, defect sites, and the oxygen evolution reaction (OER) activity of mesostructured Co3O4. High-resolution X-ray diffraction (XRD), Raman, and X-ray photoelectron spectroscopy (XPS) are consistent with the formation of cobalt vacancies at tetrahedral sites and an increase in the lattice parameter of Co3O4 after the laser treatment. X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) further reveal increased disorder in the structure and a slight decrease in the average oxidation state of the cobalt oxide. Molecular dynamics simulation confirms the surface restructuring upon laser post-treatment on Co3O4. Importantly, the defect-induced PLPP was shown to lower the charge transfer resistance and boost the oxygen evolution activity of Co3O4. For the optimized sample, a 2-fold increment of current density at 1.7 V vs RHE is obtained and the overpotential at 10 mA/cm2 decreases remarkably from 405 to 357 mV compared to pristine Co3O4. Post-mortem characterization reveals that the material retains its activity, morphology, and phase structure after a prolonged stability test.
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Jul 2021
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