Article
Chemistry, Multidisciplinary
Evgeniy Makagon, Olga Kraynis, Rotraut Merkle, Joachim Maier, Igor Lubomirsky
Summary: The study finds that doping decreases Young's modulus, and nominally dry samples generally have higher Young's modulus. All samples exhibit large non-classical electrostriction effects.
ADVANCED FUNCTIONAL MATERIALS
(2021)
Article
Chemistry, Physical
Jagoda Urban-Klaehn, Clarita Y. Regalado Vera, Radoslaw Zaleski, Hanping Ding, Hongmei Luo, Dong Ding
Summary: The study focused on defect chemistry of doped BaZrO3 proton conductors, and its findings have significant implications for proton conductivity. Using positron annihilation lifetime spectroscopy, the researchers showed that yttrium doping increased the trapping rate of positrons, while scandium doping did not have the same effect. Additionally, low-temperature hydration significantly inhibited positron trapping in the samples.
SOLID STATE IONICS
(2023)
Article
Biochemical Research Methods
Yuanxin Li, Raj Chaklashiya, Hiroki Takahashi, Yoshifumi Kawahara, Kan Tagami, Celeste Tobar, Songi Han
Summary: Magic angle spinning (MAS) nuclear magnetic resonance (NMR) experiments at ultra low temperature (ULT) have shown clear benefits for signal sensitivity gain and spin dynamics study at ULT. The addition of organic biradicals for solid-state dynamic nuclear polarization (DNP) significantly shortens the spin lattice relaxation time without broadening spectral linewidth. Experimental observations suggest bright prospects for MAS NMR and DNP under ULT conditions using closed-cycle helium MAS systems.
JOURNAL OF MAGNETIC RESONANCE
(2021)
Article
Chemistry, Physical
Andrey N. Pravdivtsev, Kai Buckenmaier, Nicolas Kempf, Gabriele Stevanato, Klaus Scheffler, Joern Engelmann, Markus Plaumann, Rainer Koerber, Jan-Bernd Hoevener, Thomas Theis
Summary: Nuclear spin hyperpolarization allows for real-time observation of metabolism and intermolecular interactions in vivo. The use of 1-13C-pyruvate as a hyperpolarized tracer is being evaluated in clinical trials and shows promise as a molecular imaging agent. However, the search for a simple, fast, and efficient hyperpolarization technique is ongoing.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Xuejiao Li, Lei Zhang, Liuming Yan, Meilin Liu, Zhongfeng Tang
Summary: In this study, reactive molecular dynamics simulations were used to investigate the defect structures and ion transport mechanism of yttrium-doped barium zirconate (BZY) electrolyte. The study found that a slightly elongated O-O distance in the hydrated system promotes proton hopping and the weak interaction between dopants and protons facilitates proton diffusion in the dislocation system. The dopant concentration and proton concentration were identified as important factors affecting proton conduction.
ACS APPLIED ENERGY MATERIALS
(2022)
Article
Chemistry, Physical
Ravi Shankar Palani, Michael Mardini, Leo Delage-Laurin, Daniel Banks, Yifu Ouyang, Eric Bryerton, James G. Kempf, Timothy M. Swager, Robert G. Griffin
Summary: In this study, selective 2H labeling of BDPA was utilized to investigate the dynamic nuclear polarization (DNP) mechanism of the Overhauser Effect (OE) in insulating solids. It was found that the alpha and gamma 1H spins on the fluorene rings were responsible for generating a positive bulk polarization, while the phenyl 1H spins contributed negative enhancements that attenuated the OE-DNP. Phenyl-d5-BDPA showed over 50% improvement in OE-DNP enhancement compared to h21-BDPA, achieving a maximum of approximately 90 at 14.1 T and 5 kHz MAS.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Biochemistry & Molecular Biology
Layane A. L. Silva, Andre A. L. Silva, Maria A. S. Rios, Manoel P. Brito, Alyne R. Araujo, Durcilene A. Silva, Ramon R. Pena-Garcia, Edson C. Silva-Filho, Janildo L. Magalhaes, Jose M. E. Matos, Josy A. Osajima, Eduardo R. Triboni
Summary: This study investigated the effects of copper doping of hydrated cobalt molybdate on its antibacterial activity and structural changes, demonstrating that increasing copper content led to larger microparticle size and better bactericidal performance against gram-positive bacteria than gram-negative bacteria. However, the use of copper as a doping agent caused an increase in the Minimum Inhibitory Concentration value in the presence of both Escherichia coli and Staphylococcus aureus strains, indicating the need for caution in utilizing copper in biocidal matrices.
Article
Chemistry, Multidisciplinary
Alexander Volkov, Jiashan Mi, Kanika Lalit, Puranjan Chatterjee, Dapeng Jing, Scott L. Carnahan, Yunhua Chen, Simin Sun, Aaron J. Rossini, Wenyu Huang, Levi M. Stanley
Summary: The library of imine-linked covalent organic frameworks (COFs) has significantly expanded in the past two decades, offering a wide range of morphologies, pore sizes, and applications. While various synthetic methods have been developed to enhance COF functionalities, most of them are specific to certain applications. This study presents a general strategy to introduce functional group handles in COFs through the Ugi multicomponent reaction, enabling the functionalization of any COFs containing imine linkages.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Michael Jurkutat, Hana Kourilova, David Peat, Karel Kouril, Alixander S. Khan, Anthony J. Horsewill, James F. MacDonald, John Owers-Bradley, Benno Meier
Summary: This study reports on the low-temperature proton spin relaxation in pyruvic acid doped with trityl at different magnetic fields, and estimates the heat capacity of the radical Non-Zeeman reservoir experimentally. The results show that the recent formalism by Wenckebach can establish a parameter-free, yet quantitative model for describing the phenomenon across the entire magnetic field range.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Nyamsuren Battumur, Nomuunaa Sergelenbaatar, Tungalagtamir Bold, Enkhsaruul Byambajav
Summary: The catalytic performance of Ni/Al, Y-doped Ni/Al-xY, and Ce-promoted Ni-yCe/Al-15Y catalysts in CO2 methanation was investigated. The increase in CO2 conversion and CH4 yield followed the order of Ni/Al < Ni/Al-5Y < Ni/Al-25Y < Ni/Al-15Y at temperatures below 350 C. The doping of gamma-Al2O3 with a moderate amount of Y improved the interaction between nickel and the support, as indicated by the higher reduction degree, H2 uptake, and total CO2 adsorption uptake of the Ni/Al-xY catalysts. Among the Ce-promoted catalysts, the Ni/Al-15Y catalyst with 2 wt% Ce exhibited the highest CO2 conversion (92.5%) and CH4 yield (92.2%) at < 350 C, attributed to the synergetic Ni-Ce interaction over the Al-15Y support.
JOURNAL OF CO2 UTILIZATION
(2023)
Article
Chemistry, Inorganic & Nuclear
Sungjun Yang, Jong Hoon Lee, Tae Joo Shin, Sangmoon Park
Summary: Oxygen vacancies in the phosphors were observed by investigating bond-length fluctuations, oxygen 1s profile, and Ge2+/Ge4+ oxidation state using synchrotron X-ray diffraction refinement, X-ray photoelectron spectroscopy, and Ge K-edge X-ray absorption near-edge structure spectra, respectively. The Ba8.8Ce0.1Na0.1Y2Ge6O24 orthogermanate phosphor, prepared by LiCl flux assistance under a reducing atmosphere, exhibited a mysterious green-yellow emission at 298 K. This emission results from the active 6-coordinated antiprism oxygen geometry around the Ce3+ ions in the phosphors.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Amrit Venkatesh, Gilles Casano, Yu Rao, Federico De Biasi, Frederic A. Perras, Dominik J. Kubicki, Didier Siri, Sebastien Abel, Hakim Karoui, Maxim Yulikov, Olivier Ouari, Lyndon Emsley
Summary: The sensitivity of NMR spectroscopy is enhanced by DNP, where polarization is transferred from unpaired electrons to proton spins in solids. The efficiency of polarization transfer near the unpaired electron spins is unclear. Experimental results and numerical simulations show that strong hyperfine couplings to nearby protons determine high transfer rates, and fewer hydrogen atoms in TEKPol isotopologues lead to longer H-1 DNP build-up times. Based on this understanding, a new biradical, NaphPol, is designed and yields significantly increased NMR sensitivity, making it the best DNP polarizing agent in organic solvents to date.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Nutrition & Dietetics
Kate M. Bermingham, Mohsen Mazidi, Paul W. Franks, Tyler Maher, Ana M. Valdes, Inbar Linenberg, Jonathan Wolf, George Hadjigeorgiou, Tim D. Spector, Cristina Menni, Jose M. Ordovas, Sarah E. Berry, Wendy L. Hall
Summary: This study characterized the variability and correlations of postprandial metabolite changes in a large cohort. The majority of metabolites showed significant changes after a meal, particularly in very large lipoprotein particles and ketone bodies. Strong correlations were observed between fasting and postprandial metabolites, although some metabolites showed weak correlations.
Review
Chemistry, Multidisciplinary
Yohei Kondo, Hiroshi Nonaka, Yoichi Takakusagi, Shinsuke Sando
Summary: Nuclear hyperpolarization is a method to enhance the sensitivity of NMR spectroscopy, allowing for highly sensitive biomedical molecular imaging. Recent development of molecular probes for hyperpolarized in vivo analysis has shown the unique metabolic and physiological information that this technique can provide.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Luke Forster, Zhipeng Qie, Min Hu, Aristarchos Mavridis, Cameron Price, Christopher M. A. Parlett, Xiaolei Fan, Carmine D'Agostino
Summary: This paper investigates the effect of different parameters on the structural properties and surface adsorption of supported solid acid catalysts. The results show that doping with STA can increase the adsorption properties of the catalyst, especially for gamma-/theta-Al2O3. Thermogravimetric analysis suggests that zirconia-grafted and non-grafted theta-Al2O3 and gamma-Al2O3 can improve the thermal stability of STA.
APPLIED SURFACE SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Jennifer P. P. Allen, Clare P. P. Grey
Summary: Dissolved transition metal ions can cause peak shifts in NMR spectra of degraded battery electrolytes. In this study, we use this simple and accessible method to calculate magnetic moments for dissolved Ni2+, Mn2+, Co2+, and Cu2+; further analysis of dissolution from LiMn2O4, LiNiO2, and LiNi0.5Mn1.5O4 reveals that the dissolved metals are exclusively divalent.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Benjamin B. Duff, Stuart J. Elliott, Jacinthe Gamon, Luke M. Daniels, Matthew J. Rosseinsky, Frederic Blanc
Summary: We used nuclear magnetic resonance approaches to determine Li-ion mobility pathways and quantify Li-ion jump rates in Li3AlS3 and Li4.3AlS3.3Cl0.7. In Li3AlS3, there are both mobile and immobile Li ions, with the latter limiting long-range translational ion diffusion. In Li4.3AlS3.3Cl0.7, a single type of fast-moving ion is present, explaining the higher conductivity of this phase.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Cameron J. J. Hargreaves, Michael W. W. Gaultois, Luke M. M. Daniels, Emma J. J. Watts, Vitaliy A. A. Kurlin, Michael Moran, Yun Dang, Rhun Morris, Alexandra Morscher, Kate Thompson, Matthew A. A. Wright, Beluvalli-Eshwarappa Prasad, Frederic Blanc, Chris M. M. Collins, Catriona A. A. Crawford, Benjamin B. B. Duff, Jae Evans, Jacinthe Gamon, Guopeng Han, Bernhard T. T. Leube, Hongjun Niu, Arnaud J. J. Perez, Aris Robinson, Oliver Rogan, Paul M. M. Sharp, Elvis Shoko, Manel Sonni, William J. J. Thomas, Andrij Vasylenko, Lu Wang, Matthew J. J. Rosseinsky, Matthew S. S. Dyer
Summary: The study presents an expert-curated dataset of lithium ion conductors and their associated conductivities. The dataset contains 820 entries collected from 214 sources, including chemical composition, structural label, and ionic conductivity at specific temperatures. Unsupervised machine learning and the Element Movers Distance were used to analyze the materials in the context of compounds from an inorganic crystal structure database. A CrabNet-based classifier was trained using this dataset to estimate the ionic conductivity of chemical compositions. This classifier serves as a practical tool for experimentalists in prioritizing candidates for further investigation as lithium ion conductors.
NPJ COMPUTATIONAL MATERIALS
(2023)
Article
Chemistry, Physical
Evelyna Wang, Erlendur Jonsson, Clare P. Grey
Summary: Similar to fuel cells, the poor mass transport of redox active species is a challenge for lithium-air batteries (LABs). In this study, nuclear magnetic resonance (NMR) spectroscopy was used to measure the concentration and transport of oxygen in LAB electrolytes, and the results were compared with values obtained from electrochemical or pressure methods. The NMR methodology was successfully used to quantify O-2 in LAB electrolytes, experimentally demonstrate solvation environments of O-2, and detect O-2 evolution in situ in a LAB flow cell.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Jennifer P. Allen, Christopher A. O'Keefe, Clare P. Grey
Summary: Transition metal dissolution is a major cause of capacity fade in lithium-ion cells, and nuclear magnetic relaxation rates can be used to quantify dissolved transition metals in battery electrolytes. This study measured relaxation rates of Li-7, P-31, F-19, and H-1 to investigate the presence of transition metals in LiPF6 electrolyte solutions. Sensitivities varied depending on the nuclide and transition metal, with F-19 and H-1 measurements showing higher sensitivity. The quantification method was found to be accurate except for heat-degraded LiPF6 electrolytes. Rating: 7/10
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Jennifer P. Allen, Clare P. Grey
Summary: NMR spectroscopy is used to evaluate the degradation of lithium-ion battery electrolyte solutions, but the presence of paramagnetic ions from cathode materials can affect the NMR spectra by inducing spectral broadening. This study investigates the effects of Ni2+ and Mn2+ on the NMR spectra of electrolyte solutions and finds that Mn2+ causes greater peak broadening than Ni2+. The 19F peaks from PF6- degradation species are most affected, followed by 31P and 1H peaks. The degree of broadening also depends on the solvent used. Mn2+ can be mitigated by diluting the electrolyte samples with a coordinating NMR solvent or by adding Li3PO4 to precipitate Mn2+ out of the solution.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Electrochemistry
Shrinidhi S. S. Pandurangi, David S. S. Hall, Clare P. P. Grey, Vikram S. S. Deshpande, Norman A. A. Fleck
Summary: Single crystal, Ni-rich layered lithium metal oxides are potential cathodes for next-generation lithium-ion batteries. However, their anisotropic swelling and contraction during cycling may lead to internal stresses, fracture, and capacity loss. This study predicts the evolution of lithium concentration and stress state within a LiNi0.8Mn0.1Co0.1O2 single crystal using a chemo-mechanical model. The results show that intraparticle fracture is not a significant degradation mode for well-designed NMC811 single crystals.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2023)
Article
Polymer Science
Chibueze V. Amanchukwu, Anna B. Gunnarsdottir, Snehashis Choudhury, Tamsin L. Newlove, Pieter C. M. M. Magusin, Zhenan Bao, Clare P. Grey
Summary: Lithium metal batteries have the potential to revolutionize energy storage and electric transportation, but face challenges in morphology and electro-chemo-mechanics. Polymer-based solid-state electrolytes show promise in replacing liquid electrolytes, but have issues with ionic conductivity and stability. Perfluoropolyether (PFPE)-based electrolytes have improved oxidative stability, but little is known about their lithium solvation and transport mechanism. This study uses solid-state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy to investigate lithium cation environment and mobility in PFPE electrolytes and compare it to polyethylene glycol (PEG) electrolytes. The results show weaker interaction between lithium cation and PFPE polymer backbone, resulting in stronger ion pairing. The mobility of lithium ions is lower in PFPE electrolytes, attributed to polymer backbone fluctuations. Differences in polymer backbones have a greater effect on mobility than differences in ion binding modes within each polymer class. The ability to study polymer electrolytes in their native state opens opportunities for development of next-generation lithium metal batteries.
Article
Chemistry, Multidisciplinary
Lucia Corti, Dinu Iuga, John B. Claridge, Matthew J. Rosseinsky, Frederic Blanc
Summary: This study presents a combined experimental and computational approach to investigate the local configurational disorder and oxide ion diffusion mechanism in layered tetrahedral network melilite. The results obtained from MAS NMR spectroscopy provide evidence of the conduction mechanism and highlight the potential of this technique in enhancing the understanding of ionic motion in solid electrolytes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Rory C. McNulty, Elizabeth Hampson, Lewis N. Cutler, Clare P. Grey, Wesley M. Dose, Lee R. Johnson
Summary: As state-of-the-art lithium-ion intercalation materials like nickel-rich chemistries are being pushed to their limits, understanding specific degradation and performance limitations becomes crucial. Half-cells, commonly used in industry and academia, are limited by the reactivity of lithium metal, which leads to early electrolyte degradation and cell failure. In this study, the limitations of half-cell studies of NMC811 electrodes with commercial loading are investigated, and it is found that the presence of Li has a detrimental impact on the NMC811 chemistry. The use of Li4Ti5O12 (LTO) as an alternative counter electrode is proposed for studying NMC positive electrode materials due to its high coulombic efficiency and low reactivity.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Cassius Clark, Christopher A. O'Keefe, Dominic S. Wright, Clare P. Grey
Summary: By optimizing the annealing time, nitrogen-doped graphitic spheres (NDGSs) with high nitrogen content were fabricated. These NDGSs exhibited stable bulk nitrogen doping level of 9% and performed well as anodes in lithium-ion batteries. However, they did not perform well in sodium-ion batteries.
Article
Chemistry, Physical
Jennifer P. Allen, Clare P. Grey
Summary: NMR spectroscopy is used to evaluate degradation of lithium-ion battery electrolyte solutions, but the presence of paramagnetic ions may affect the NMR spectra, inducing spectral broadening. This study investigates how dissolved Ni2+ and Mn2+ ions in LiPF6 electrolyte solutions affect the NMR spectra of pristine and degraded electrolyte solutions, and finds that Mn2+ causes greater broadening than Ni2+. The paramagnetic metals mainly affect the peak intensities of PF6- degradation species, followed by 31P and 1H peaks. The degree of broadening is solvent-dependent and can be mitigated by using a solvent with higher donor number. Dilution with a coordinating NMR solvent is effective in minimizing broadening caused by dissolved Mn2+. Li3PO4 addition also helps restore spectral resolution by precipitating Mn2+ out of the electrolyte samples.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Jana B. Fritzke, James H. J. Ellison, Laurence Brazel, Gabriela Horwitz, Svetlana Menkin, Clare P. Grey
Summary: This article discusses the experimental approaches developed by the authors to understand the function and failure of lithium-oxygen batteries. It covers various experiments including the use of nuclear magnetic resonance spectroscopy to quantify dissolved oxygen concentrations, the study of electrolyte decomposition products, and the use of redox mediators to prevent electrode clogging and improve battery performance.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Physical
Sundeep Vema, Astrid H. Berge, Supreeth Nagendran, Clare P. Grey
Summary: The localization and site occupancy of dopants in LLZO are not fully understood, and this study shows that Al and Ga only occupy the 24d site in the lattice. Formation of side products can consume Al/Ga dopants and influence the lithium-ion conductivity in LLZO.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Laura L. Driscoll, Elizabeth H. Driscoll, Bo Dong, Farheen N. Sayed, Jacob N. Wilson, Christopher A. O'Keefe, Dominic J. Gardner, Clare P. Grey, Phoebe K. Allan, Adam A. L. Michalchuk, Peter R. Slater
Summary: The synthesis of Li ion battery materials via ball milling has seen significant growth, resulting in the discovery of new high-capacity electrode materials. This study challenges the commonly assumed local heating effects during the milling process, showing that other factors, such as shockwaves and localized pressure, play a crucial role in phase transformations. The research provides a greater understanding of milling as a synthetic pathway and suggests alternative strategies for material preparation.
ENERGY & ENVIRONMENTAL SCIENCE
(2023)