Restructuring Co-CoOx Interface with Titration Rate in Co/Nb-CeO2 Catalysts for Higher Water-Gas Shift Performance.

H2 production via water-gas shift reaction (WGS) is an important process and applied widely. Cobalt-modified CeO2 are promising catalysts for WGS reaction. Herein, a series of Co/Nb-CeO2 catalysts were prepared by varying the rate of precipitant addition during the coprecipitation method and examined for hydrogen generation through WGS reaction. The rates of precipitant addition were 1, 5, 15, and 25 mL/min. We obtained ceria supported cobalt catalysts with different sizes and morphology such as 3, 8 nm nanoclusters, 30 nm cubic nanoparticles, and 50 nm hexagonal nanoparticles. The well dispersed small cobalt particles in Co/Nb-CeO2 that was prepared at 5 mL/min titration rate exhibit strong interaction between cobalt oxide and CeO2 that retards the reduction of CoOx producing Co-CoOx pairs. In contrast, 1-Co/Nb-CeO2 and 25-Co/Nb-CeO2 result in bigger and aggregated Co particles, resulting in fewer interfaces with CeO2. The Co0, Coδ+, Ce3+, and Ov species are responsible for improved reducibility in Co/Nb-CeO2 catalysts and were quantitively measured using XPS, XAS, and Raman spectroscopy. The Co-CoOx interface assists dissociation of the H2O molecule; CO oxidation requires low activation energy and realizes a high turnover frequency of 9.8 s-1. The 5-Co/Nb-CeO2 catalyst achieved thermodynamic equilibrium equivalent CO conversion with efficient H2 production during WGS reaction at a gas hourly space velocity of 315,282 h-1. Successively, the 5-Co/Nb-CeO2 catalyst exhibited stable performance for straight 168 h attributed to stable CO-Coδ+ intermediate formation, achieving efficient inhibition of typical CO chemistry over the Co metal, suitable for hydrogen generation from waste derived synthesis gas.

Extratendinous migration of calcific tendinitis of the rotator cuff: imaging findings and clinical characteristics with temporal changes.

PURPOSE: The aim of this study was to analyze the imaging findings and clinical characteristics of extratendinous migration of calcific tendinitis of the shoulder with temporal changes. METHODS: Seventy-six patients with extratendinous calcific tendinitis of the shoulder diagnosed by ultrasonography (US) or magnetic resonance imaging (MRI) were enrolled in this retrospective study. Clinical symptoms and imaging findings (on radiography, US, and MRI) of extratendinous calcific tendinitis during an acute painful attack were analyzed. Temporal changes were analyzed in 28 patients before an acute attack and 40 patients after an acute attack. For comparison, 65 patients with intratendinous calcific tendinitis were included. RESULTS: Patients with extratendinous calcific tendinitis had a significantly higher average visual analogue scale (VAS) score (8.8±1.6) than the intratendinous group (6.4±2.2) (P<0.001). The fragmented type (80.5%) was the most common shape on US; sonographic black hole appearance (14.6%) and echogenic fluid (9.8%) were characteristic findings of intrabursal calcifications. In 28 patients with previous radiographs, radiographic type III (78.6%) was dominant and the location of calcific deposits changed (82.1%) during the acute painful attack, which was also perceivable in 12 patients with previous US or MRI. In follow-up radiographs of 40 patients, calcifications shrunk by more than 50% or became invisible in 82.5% of patients, with symptom improvement (VAS score, 8.9±1.5 to 1.9±1.2). Follow-up US and MRI of 16 patients also showed decreased size (56.3%) or disappearance (43.7%) of calcific deposits. CONCLUSION: Extratendinous calcific tendinitis has distinctive imaging features, the temporal changes of which correlate well with clinical symptoms.

Periosteal autograft for articular cartilage defects in dogs: MR imaging and ultrasonography of the repair process.

BACKGROUND: Autologous periosteal grafting is used as treatment for cartilage defects. PURPOSE: To assess the role of MR imaging and ultrasonography in the evaluation of the post-graft repair process with imaging and histologic correlation. MATERIAL AND METHODS: Periosteal grafts obtained from the tibia of eight dogs were transplanted to the experimental cartilage defects in the femoral condyles (15 knees). The control group was comprised of three dogs (five knees). MR imaging using 4.7T and ultrasonography of the grafted specimens was performed at one, two, four, eight, and 16 weeks after transplantation. The animals were sacrificed at the time of imaging at the previously specified intervals. Histologic analysis with imaging correlation was subsequently performed. RESULTS: All specimens taken from one to 16 weeks demonstrated periosteal proliferation in the graft. At one week, experimental cartilage defects were no longer present on MR imaging. Area of high signal intensity (SI) in the defect was present which corresponded to hemorrhage, edema, and fibrosis on histology. At two, four, and eight weeks, all but two graft demonstrated heterogeneous high SI on T2-weighted image, consistent with immature cartilage. At 16 weeks, all grafts showed heterogeneous isointense to adjacent cartilage on all sequences, which corresponded to dominant mature cartilage. The repair tissue near the exposed subchondral bone revealed heterogeneous high SI on T2-weighted images. This corresponded to the fibrosis with vascular penetration and edema. In the control group, no cartilage repair was noted within cartilage defects. The serial MR features of the grafted area correlated well with the histologic findings. Serial sonographic findings were not sufficient to provide the regenerated cartilage maturity. CONCLUSION: MR imaging is capable of depicting the repair characteristics following periosteal grafting for articular cartilage defects. MR imaging may provide useful information in the assessment of the graft appearance with definite implications regarding the degree and success of incorporation.