Do observations on surface coverage-reactivity correlations always describe the true catalytic process? A case study on ceria

In situ (operando) investigations aim at establishing structure-function and/or coverage-reactivity correlations. Herein, we investigated the gas-phase HCl oxidation (4HCl + O2 → 2Cl2 + 2H2O) over ceria. Despite its remarkable performance, under low oxygen over-stoichiometry, this oxide is prone to a certain extent to subsurface/bulk chlorination, which leads to deactivation. In situ Prompt Gamma Activation Analysis (PGAA) studies evidenced that the chlorination rate is independent of the pre-chlorination degree but increases at lower oxygen over-stoichiometry, while dechlorination is effective in oxygen-rich feeds, and its rate is higher for a more extensively pre-chlorinated ceria. Even bulk CeCl3 could be transformed into CeO2 under oxygen excess. Electron Paramagnetic Resonance experiments strongly suggested that oxygen activation is inhibited by a high surface chlorination degree. The coverages of most abundant surface intermediates, OH and Cl, were monitored by in situ infrared spectroscopy and PGAA under various conditions. Higher temperature and p(O2) led to enhanced OH coverage, reduced Cl coverage, and increased reactivity. Variation of p(HCl) gave rise to opposite correlations, while raising p(Cl2) did not induce any measurable increase in the Cl coverage, despite the strong inhibition of the reaction rate. The results indicate that only a small fraction of surface sites is actively involved in the reaction, and most of the surface species probed in the in situ observation are spectators. Therefore, when performing in situ steady-state experiments, a large set of variables should be considered to obtain accurate conclusions

Performance, structure, and mechanism of CeO₂ in HCl oxidation to Cl₂

Experimental and theoretical studies reveal performance descriptors and provide molecular-level understanding of HCl oxidation over CeO2. Steady-state kinetics and characterization indicate that CeO2 attains a significant activity level, which is associated with the presence of oxygen vacancies. Calcination of CeO2 at 1173 K prior to reaction maximizes both the number of vacancies and the structural stability of the catalyst. X-ray diffraction and electron microscopy of samples exposed to reaction feeds with different O2/HCl ratios provide evidence that CeO2 does not suffer from bulk chlorination in O2-rich feeds (O2/HCl ≥ 0.75), while it does form chlorinated phases in stoichiometric or sub-stoichiometric feeds (O2/HCl ≤ 0.25). Quantitative analysis of the chlorine uptake by thermogravimetry and X-ray photoelectron spectroscopy indicates that chlorination under O2-rich conditions is limited to few surface and sub-surface layers of CeO2 particles, in line with the high energy computed for the transfer of Cl from surface to sub-surface positions. Exposure of chlorinated samples to a Deacon mixture with excess oxygen rapidly restores the original activity levels, highlighting the dynamic response of CeO2 outermost layers to feeds of different composition. Density functional theory simulations reveal that Cl activation from vacancy positions to surface Ce atoms is the most energy-demanding step, although chorine-oxygen competition for the available active sites may render re-oxidation as the rate-determining step. The substantial and remarkably stable Cl2 production and the lower of CeO2 make it an attractive alternative to RuO2 for catalytic chlorine recycling in industry

Demonstration of a Longitudinal Action Medical Mission (LAMM) Model to Teach Point-of-Care Ultrasound in Resource-Limited Settings

BACKGROUND: Short-term medical missions prevail as the most common form of international medical volunteerism, but they are ill-suited for medical education and training local providers in resource-limited settings. OBJECTIVE: The purpose of this study is to evaluate the effectiveness of a longitudinal educational program in training clinicians how to perform point-of-care ultrasound (POCUS) in resource-limited clinics. DESIGN: A retrospective study of such a four-month POCUS training program was conducted with clinicians from a rural hospital in Haiti. The model included one-on-one, in-person POCUS teaching sessions by volunteer instructors from the United States and Europe. The Haitian trainees were assessed at the start of the program and at its conclusion by a direct objective structured clinical examination (OSCE), administered by the visiting instructors, with similar pre- and post- program ultrasound competency assessments. RESULTS: Post-intervention, a significant improvement was observed (p < 0.0001), and each trainee showed significant overall improvement in POCUS competency independent of the initial competency pre-training (p < 0.005). There was a statistically significant improvement in POCUS application for five of the six medically relevant assessment categories tested. CONCLUSION: Our results provide a proof-of-concept for the longitudinal education-centered healthcare delivery framework in a resource-limited setting. Our longitudinal model provides local healthcare providers the skills to detect and diagnose significant pathologies, thereby reducing avoidable morbidity and mortality at little or no addition cost or risk to the patient. Furthermore, training local physicians obviates the need for frequent volunteering trips, saving costs in healthcare training and delivery

Lars Hætta’s miniature world: Sámi prison op-art autoethnography

This article examines a collection of miniature objects, now held in museum collections, which were originally made by a Sámi political prisoner in Norway during the mid-19th century as part of an educational programme. The author draws on recent developments in the theory of miniaturization to consider these miniatures as examples of prison op-art autoethnography: communicative devices which seek to address broad and complex social issues through the process of the creation and distribution of semiophorically functionless mimetic objects of reduced scale and complexity, and which reflect the restrictions of incarcerated artistic expression and the questions this raises regarding authenticity and hybridity

The solvation and dissociation of 4-benzylaniline hydrochloride in chlorobenzene

A reaction scheme is proposed to account for the liberation of 4-benzylaniline from 4-benzylaniline hydrochloride, using chlorobenzene as a solvent at a temperature of 373 K. Two operational regimes are explored: “closed” reaction conditions correspond to the retention of evolved hydrogen chloride gas within the reaction medium, whereas an “open” system permits gaseous hydrogen chloride to be released from the reaction medium. The solution phase chemistry is analyzed by 1H NMR spectroscopy. Complete liberation of solvated 4-benzylaniline from solid 4-benzylaniline hydrochloride is possible under “open” conditions, with the entropically favored conversion of solvated hydrogen chloride to the gaseous phase thought to be the thermodynamic driver that effectively controls a series of interconnecting equilibria. A kinetic model is proposed to account for the observations of the open system

Dimerization of FIR upon FUSE DNA binding suggests a mechanism of c-myc inhibition

c-myc is essential for cell homeostasis and growth but lethal if improperly regulated. Transcription of this oncogene is governed by the counterbalancing forces of two proteins on TFIIH—the FUSE binding protein (FBP) and the FBP-interacting repressor (FIR). FBP and FIR recognize single-stranded DNA upstream of the P1 promoter, known as FUSE, and influence transcription by oppositely regulating TFIIH at the promoter site. Size exclusion chromatography coupled with light scattering reveals that an FIR dimer binds one molecule of single-stranded DNA. The crystal structure confirms that FIR binds FUSE as a dimer, and only the N-terminal RRM domain participates in nucleic acid recognition. Site-directed mutations of conserved residues in the first RRM domain reduce FIR's affinity for FUSE, while analogous mutations in the second RRM domain either destabilize the protein or have no effect on DNA binding. Oppositely oriented DNA on parallel binding sites of the FIR dimer results in spooling of a single strand of bound DNA, and suggests a mechanism for c-myc transcriptional control