Solid‐state lithium batteries will revolutionize the lithium‐ion battery and energy storage applications if certain key challenges can be resolved. The formation of lithium‐protrusions (dendrites) that can cause catastrophic short‐circuiting is one of the main obstacles, and progresses by a mechanism that is not yet fully understood. By utilizing X‐ray computed tomography with nanoscale resolution, the 3D morphology of lithium protrusions inside short‐circuited solid electrolytes has been obtained for the first time. Distinguishable from adjacent voids, lithium protrusions partially filled cracks that tended to propagate intergranularly through the solid electrolyte, forming a large waved plane in the shape of the grain boundaries. Occasionally, the lithium protrusions bifurcate into flat planes in a transgranular mode. Within the cracks themselves, lithium protrusions are preferentially located in regions of relatively low curvature. The crack volume filled with lithium in two samples is 82.0% and 83.1%, even though they have distinctly different relative densities. Pre‐existing pores in the solid electrolyte, as a consequence of fabrication, can also be part‐filled with lithium, but do not have a significant influence on the crack path. The crack/lithium‐protrusion behavior qualitatively supports a model of propagation combining electrochemical and mechanical effects.
Octopus (Optics Clustered to OutPut Unique Solutions) celebrated in June 2020 its 10th birthday. Based at Harwell, near Oxford, Octopus is an open access, peer reviewed, national imaging facility that offers successful U.K. applicants supported access to single molecule imaging, confocal microscopy, several flavours of superresolution imaging, light sheet microscopy, optical trapping and cryoscanning electron microscopy. Managed by a multidisciplinary team, Octopus has so far assisted >100 groups of U.K. and international researchers. Cross‐fertilisation across fields proved to be a strong propeller of success underpinned by combining access to top‐end instrumentation with a strong programme of imaging hardware and software developments. How Octopus was born, and highlights of the multidisciplinary output produced during its 10‐year journey are reviewed below, with the aim of celebrating a myriad of collaborations with the U.K. scientific community, and reflecting on their scientific and societal impact.
We present Parameter Quantification Network (PQ-Net), a regression deep convolutional neural network providing quantitative analysis of powder X-ray diffraction patterns from multi-phase systems. The network is tested against simulated and experimental datasets of increasing complexity with the last one being an X-ray diffraction computed tomography dataset of a multi-phase Ni-Pd/CeO2-ZrO2/Al2O3 catalytic material system consisting of ca. 20,000 diffraction patterns. It is shown that the network predicts accurate scale factor, lattice parameter and crystallite size maps for all phases, which are comparable to those obtained through full profile analysis using the Rietveld method, also providing a reliable uncertainty measure on the results. The main advantage of PQ-Net is its ability to yield these results orders of magnitude faster showing its potential as a tool for real-time diffraction data analysis during in situ/operando experiments.
Nature employs high-energy metal-oxo intermediates embedded within enzyme active sites to perform challenging oxidative transformations with remarkable selectivity. Understanding how different local metal-oxo coordination environments control intermediate reactivity and catalytic function is a long-standing objective. However, conducting structure–activity relationships directly in active sites has proven challenging due to the limited range of amino acid substitutions achievable within the constraints of the genetic code. Here, we use an expanded genetic code to examine the impact of hydrogen bonding interactions on ferryl heme structure and reactivity, by replacing the N–H group of the active site Trp51 of cytochrome c peroxidase by an S atom. Removal of a single hydrogen bond stabilizes the porphyrin π-cation radical state of CcP W191F compound I. In contrast, this modification leads to more basic and reactive neutral ferryl heme states, as found in CcP W191F compound II and the wild-type ferryl heme-Trp191 radical pair of compound I. This increased reactivity manifests in a >60-fold activity increase toward phenolic substrates but remarkably has negligible effects on oxidation of the biological redox partner cytc. Our data highlight how Trp51 tunes the lifetimes of key ferryl intermediates and works in synergy with the redox active Trp191 and a well-defined substrate binding site to regulate catalytic function. More broadly, this work shows how noncanonical substitutions can advance our understanding of active site features governing metal-oxo structure and reactivity.
A polymer electrolyte fuel cell (PEFC) has been designed to allow operando X-ray
absorption spectroscopy (XAS) measurements of catalysts. The cell has been developed to
operate under standard fuel cell conditions, with elevated temperatures and humidification of
the gas-phase reactants, both of which greatly impact the catalyst utilisation. X-ray windows
in the endplates of the cell facilitate collection of XAS spectra during fuel cell operation
while maintaining good compression in the area of measurement. Results of polarisation
curves and cyclic voltammograms (CVs) showed that the operando cell performs well as a
fuel cell, while also providing XAS data of suitable quality for robust XANES analysis. The
cell has produced comparable XAS results when performing a cyclic voltammogram to an
established in situ cell when measuring the Pt LIII edge. Similar trends of Pt oxidation, and
reduction of the formed Pt oxide, have been presented with a time resolution of 5 seconds for
each spectrum, paving the way for time-resolved spectral measurements of fuel cell catalysts
in a fully-operating fuel cell
Rapidly increasing anthropogenic carbon dioxide (CO2) emissions, coupled with irreversible climate change and depleting fossil fuel reserves, have significantly increased the drive for CO2 utilisation. Iron sulfide as a catalyst for the hydrogenation of CO2 has been discussed in the literature for decades, especially in an origin-of-life context, but little experimental evidence exists in the literature for its feasibility. Here we report the catalytic properties of pyrrhotite (Fe1−xS) for the hydrogenation of CO2 into formate. Advanced material characterisation methods in combination with computational studies have allowed us to identify surface S–Fe–O moieties as active sites for the reaction.