Ceria nanocrystallites with different morphologies and crystal planes were hydrothermally prepared, and the effects of ceria supports on the physicochemical and catalytic properties of Pd/CeO 2 for the CO and propane oxidation were examined. The results showed that the structure and chemical state of Pd on ceria were affected by ceria crystal planes. The Pd species on CeO 2 -R (rods) and CeO 2 -C (cubes) mainly formed Pd x Ce 1−x O 2−σ solid solution with −Pd 2+ −O 2− −Ce 4+ − linkage. In addition, the PdO x nanoparticles were dominated on the surface of Pd/CeO 2 -O (octahedrons). For the CO oxidation, the Pd/CeO 2 -R catalyst showed the highest catalytic activity among three catalysts, its reaction rate reached 2.07 × 10 −4 mol g Pd −1 s −1 at 50 °C, in which CeO 2 -R mainly exposed the ( 110) and (100) facets with low oxygen vacancy formation energy, strong reducibility, and high surface oxygen mobility. TOF of Pd/CeO 2 -R (3.78 × 10 −2 s −1 ) was much higher than that of Pd/CeO 2 -C (6.40 × 10 −3 s −1 ) and Pd/CeO 2 -O (1.24 × 10 −3 s −1 ) at 50 °C, and its activation energy (E a ) was 40.4 kJ/mol. For propane oxidation, the highest reaction rate (8.08 × 10 −5 mol g Pd −1 s −1 at 300 °C) was obtained over the Pd/CeO 2 -O catalyst, in which CeO 2 -O mainly exposed the (111) facet. There are strong surface Ce−O bonds on the ceria (111) facet, which favors the existence of PdO particles and propane activation. The turnover frequency (TOF) of the Pd/CeO 2 -O catalyst was highest (3.52 × 10 −2 s −1 ) at 300 °C and its E a value was 49.1 kJ/mol. These results demonstrate the inverse facet sensitivity of ceria for the CO and propane oxidation over Pd/ ceria.
There is a need to find better strategies to promote wound healing, especially of chronic wounds, which remain a challenge. We found that synovium mesenchymal stem cells (SMSCs) have the ability to strongly promote cell proliferation of fibroblasts; however, they are ineffective at promoting angiogenesis. Using gene overexpression technology, we overexpressed microRNA‐126‐3p (miR‐126‐3p) and transferred the angiogenic ability of endothelial progenitor cells to SMSCs, promoting angiogenesis. We tested a therapeutic strategy involving controlled‐release exosomes derived from miR‐126‐3p‐overexpressing SMSCs combined with chitosan. Our in vitro results showed that exosomes derived from miR‐126‐3p‐overexpressing SMSCs (SMSC‐126‐Exos) stimulated the proliferation of human dermal fibroblasts and human dermal microvascular endothelial cells (HMEC‐1) in a dose‐dependent manner. Furthermore, SMSC‐126‐Exos also promoted migration and tube formation of HMEC‐1. Testing this system in a diabetic rat model, we found that this approach resulted in accelerated re‐epithelialization, activated angiogenesis, and promotion of collagen maturity in vivo. These data provide the first evidence of the potential of SMSC‐126‐Exos in treating cutaneous wounds and indicate that modifying the cells—for example, by gene overexpression—and using the exosomes derived from these modified cells provides a potential drug delivery system and could have infinite possibilities for future therapy. Stem Cells Translational Medicine
2017;6:736–747
The doping of In2O3 significantly promoted
the catalytic performance of Co3O4 for CO oxidation.
The activities of In2O3–Co3O4 increased with an increase in In2O3 content, in the form of a volcano curve. Twenty-five wt % In2O3–Co3O4 (25 InCo)
showed the highest CO oxidation activity, which could completely convert
CO to CO2 at a temperature as low as −105 °C,
whereas it was only −40 °C over pure Co3O4. The doping of In2O3 induced the expansion
of the unit cell and structural distortion of Co3O4, which was confirmed by the slight elongation of the Co–O
bond obtained from EXAFS data. The red shift of the UV–vis
absorption illustrated that the electron transfer from O2– to Co3+/Co2+ became easier and implied that
the bond strength of Co–O was weakened, which promoted the
activation of oxygen. Low-temperature H2-TPR and O2-TPD results also revealed that In2O3–Co3O4 behaved with excellent redox
ability. The XANES, XPS, XPS valence band, and FT-IR data exhibited
that the CO adsorption strength became weaker due to the downshift
of the d-band center, which correspondingly weakened the adsorption
of CO2 and obviously inhibited the accumulation of surface
carbonate species. In short, the doping of In2O3 induced the structural defects, modified the surface electronic
structure, and promoted the redox ability of Co3O4, which tuned the adsorption strength of CO and oxygen activation
simultaneously.
Using density functional theory with the inclusion of on-site Coulomb correction, the O vacancy formation energies of Ce
x
Zr1−x
O2 solid solutions with a series of Ce/Zr ratios are calculated, and a model to understand the results is proposed. It consists of electrostatic and structural relaxation terms, and the latter is found to play a vital role in affecting the O vacancy formation energies. Using this model, several long-standing questions in the field, such as why ceria with 50% ZrO2 usually exhibit the best oxygen storage capacity, can be explained. Some implications of the new interpretation are also discussed.
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