Atoms on the edge: The atomic edge structure of industrial‐style MoS2 nanocatalysts was imaged using single‐atom sensitive electron microscopy (see picture). The observed industrial‐style edge terminations match predictions of model catalyst studies and thus address the so‐called “materials gap” in catalysis.
The functional properties of transition metal dichalcogenides (TMDs) may be promoted by the inclusion of other elements. Here, we studied the local stoichiometry of single cobalt promoter atoms in an industrial-style MoS2-based hydrotreating catalyst. Aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy show that the Co atoms occupy sites at the (-100) S edge terminations of the graphite-supported MoS2 nanocrystals in the catalyst. Specifically, each Co atom has four neighboring S atoms that are arranged in a reconstructed geometry, which reflects an equilibrium state. The structure agrees with complementary studies of catalysts that were prepared under vastly different conditions and on other supports. In contrast, a small amount of residual Fe in the graphite is found to compete for the S edge sites, so that promotion by Co is strongly sensitive to the purity of the raw materials. The present single-atom-sensitive analytical method therefore offers a guide for advancing preparative methods for promoted TMD nanomaterials.
Transmission electron microscopy (TEM) is used to study growth of MoS2 nanocrystals in situ. The nanocrystals are formed from a submonolayer molybdenum oxide dispersed on an oxide support by sulfidation in an H2S/H2 atmosphere. From series of time-resolved TEM images, it is revealed that single-layer MoS2 nanocrystals form preferentially and that multi-layer nanocrystals form late in the sulfidation process. The TEM images pinpoint that step sites in the support can act as nucleation centers for single-layer nanocrystals and that single-layer nanocrystals grow along the support surface. Moreover, the TEM images reveal that multi-layer MoS2 nanocrystals form in a layer-by-layer mode by the homogeneous nucleation of additional MoS2 layers onto already formed single-layer MoS2 nanocrystals. Hereby, the atomic-scale observations suggest that the formation of multi-layer MoS2 nanocrystals is an energetically more activated process than growth of single-layers. These findings explain why process parameters, such as temperature, can tune the relative fraction of single- to multi-layer MoS2 nanocrystals, which is important for their use in, e.g., hydrotreating catalysis.
Background:Plantar fasciitis (PF) affects 7% to 10% of the population. The long-term prognosis is unknown.Purpose:Our study had 4 aims: (1) to assess the long-term prognosis of PF, (2) to evaluate whether baseline characteristics (sex, body mass index, age, smoking status, physical work, exercise-induced symptoms, bilateral heel pain, fascia thickness, and presence of a heel spur) could predict long-term outcomes, (3) to assess the long-term ultrasound (US) development in the fascia, and (4) to assess whether US-guided corticosteroid injections induce atrophy of the heel fat pad.Study Design:Cohort study; Level of evidence, 3.Methods:From 2001 to 2011 (baseline), 269 patients were diagnosed with PF based on symptoms and US. At follow-up (2016), all patients were invited to an interview regarding their medical history and for clinical and US re-examinations. Kaplan-Meier survival estimates were used to estimate the long-term prognosis, and a multiple Cox regression analysis was used for the prediction model.Results:In all, 174 patients (91 women, 83 men) participated in the study. All were interviewed, and 137 underwent a US examination. The mean follow-up was 9.7 years from the onset of symptoms and 8.9 years from baseline. At follow-up, 54% of patients were asymptomatic (mean duration of symptoms, 725 days), and 46% still had symptoms. The risk of having PF was 80.5% after 1 year, 50.0% after 5 years, 45.6% after 10 years, and 44.0% after 15 years from the onset of symptoms. The risk was significantly greater for women (P < .01) and patients with bilateral pain (P < .01). Fascia thickness decreased significantly in both the asymptomatic and symptomatic groups (P < .01) from 6.9 mm and 6.7 mm, respectively, to 4.3 mm in both groups. Fascia thickness (P = .49) and presence of a heel spur (P = .88) at baseline had no impact on prognosis. At follow-up, fascia thickness and echogenicity had normalized in only 24% of the asymptomatic group. The mean fat pad thickness was 9.0 mm in patients who had received a US-guided corticosteroid injection and 9.4 mm in those who had not been given an injection (P = .66).Conclusion:The risk of having PF in this study was 45.6% at a mean 10 years after the onset of symptoms. The asymptomatic patients had PF for a mean 725 days. The prognosis was significantly worse for women and patients with bilateral pain. Fascia thickness decreased over time regardless of symptoms and had no impact on prognosis, and neither did the presence of a heel spur. Only 24% of asymptomatic patients had a normal fascia on US at long-term follow-up. A US-guided corticosteroid injection did not cause atrophy of the heel fat pad. Our observational study did not allow us to determine the efficacy of different treatment strategies.
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