Directionally In Situ Self-Assembled, High-Density, Macropore-Oriented, CoP-Impregnated, 3D Hierarchical Porous Carbon Sheet Nanostructure for Superior Electrocatalysis in the Hydrogen Evolution Reaction.

3D ZIF-67-particles-impregnated cellulose-nanofiber nanosheets with oriented macropores are synthesized via directional-freezing-assisted in situ self-assembly, and converted to 3D CoP-nanoparticle (NP)-embedded hierarchical, but macropores-oriented, N-doped carbon nanosheets via calcination and phosphidation. The obtained nanoarchitecture delivers overpotentials at 10 and 50 mA cm-2 and Tafel slope of 82.1 and 113.4 mV and 40.8 mV dec-1 in 0.5 M H2 SO4 , and of 97.1 and 136.6 mV and 51.2 mV dec-1 in 1 M KOH, all of which are superior to those of the most reported non-noble-metal-based hydrogen evolution reaction (HER) catalysts. This catalyst even surpasses commercial Pt/C for a much lower overpotential at high current densities, which is essential for large-scale hydrogen production. Its catalytic activity can be further optimized to become one of the best in both 0.5 M H2 SO4 and 1 M KOH. The outstanding catalytic activity is ascribed to the uniformly-dispersed small CoP NPs in the 3D carbon sheets and the hierarchical nanostructure with rich oriented pores. This work develops a facile, economical, and universal self-assembly strategy to fabricate uniquely nanostructured hybrids to simultaneously promote charge transfer and mass transport, and also offers an inexpensive and high-performance HER catalyst toward industry-scale water splitting.

Effect of a novel pretreatment on the microtensile bond strength of universal adhesives with dentin.

Background: /purpose: The quality of the hybrid layer is of great importance for dentin bonding. The purpose of this study was to develop a novel copper-based pretreatment and investigate the effect of the pretreatment combined with universal adhesives on the dentin bond strength. Materials and methods: Etch-and-rinse adhesive Single Bond 2 (SB2) and two universal adhesives Prime Bond Universal (PBU) and Single Bond Universal (SBU) were selected. The dentin surfaces were pretreated with CuSO4 solution and K2HPO4 solution in turn (Cu-P pretreatment), and the adhesive was applied following the manufacturer's instructions. There were four groups of Cu-P pretreatment: HH-Cu (1.5 mol/L CuSO4 + 1.0 mol/L K2HPO4); H-Cu (0.15 mol/L CuSO4 + 0.1 mol/L K2HPO4); L-Cu (0.015 mol/L CuSO4 + 0.01 mol/L K2HPO4); and LL-Cu (0.0015 mol/L CuSO4 + 0.001 mol/L K2HPO4). The microtensile bond strength (µ-TBS) and fracture mode were determined. The dentin surface after pretreatment and the antimicrobial properties of the pretreatment agent were also evaluated. Results: The minimum inhibitory concentration and minimum bactericidal concentration of Cu-P pretreatment were 0.012 mol/L CuSO4 + 0.008 mol/L K2HPO4. Combined with SB2, the H-Cu and L-Cu groups showed a higher µ-TBS (P < 0.01), while the HH-Cu group showed a lower µ-TBS (P < 0.001), and the LL-Cu group showed a similar µ-TBS with the control group without Cu-P pretreatment. Combined with universal adhesives PBU and SBU, the H-Cu and L-Cu groups also showed significantly increased µ-TBS (P < 0.01). Conclusion: The copper-based pretreatment in combination with universal adhesives improved the dentin microtensile bond strength.

Three-dimensional Ni foam supported NiCoO2@Co3O4 nanowire-on-nanosheet arrays with rich oxygen vacancies as superior bifunctional catalytic electrodes for overall water splitting.

Earth abundant transition metal oxide (EATMO)-based bifunctional catalysts for overall water splitting are highly desirable, but their performance is far from satisfactory due to low intrinsic activities of EATMOs toward electrocatalysis of both oxygen and hydrogen evolution reactions and poor electron transfer and transport capabilities. A three-dimensional (3-D) Ni-foam-supported NiCoO2@Co3O4 nanowire-on-nanosheet heterostructured array with rich oxygen vacancies has been synthesized, showing OER activity superior to most reported catalysts and even much higher than Ru and Ir-based ones and HER activity among the highest reported for non-noble-metal-based catalysts. The excellent activities are ascribed to the highly dense, ultrathin nanowire arrays epitaxially grown on an interconnected layered nanosheet array greatly facilitating electron transfer and providing numerous electrochemically accessible active sites and the high content of oxygen vacancies on nanowires greatly promoting OER and HER. When adopted as bifunctional electrodes for overall water splitting, this heterostructure shows an overvoltage (at 10 mA cm-2) lower than most reported electrolyzers and high stability. This work not only creates a 3-D EATMO-based integrated heterostructure as a low-cost, highly efficient bifunctional catalytic electrode for water splitting, but also provides a novel strategy to use unique heteronanostructures with rich surface defects for synergistically enhancing electrocatalytic activities.

Effectiveness of different cleaning measures on the bonding of resin cement to saliva-contaminated or blood-contaminated zirconia.

OBJECTIVE: To investigate the effectiveness of different cleaning measures on the bonding of resin cement to saliva- or blood-contaminated zirconia. METHODS: One hundred and forty-one specimens (10 × 10 × 1.5 mm3) were fabricated from KATANATM zirconia blocks and contaminated with human saliva or sheep blood. Six cleaning measures were examined: water-rinse, H3PO4, 5.25% NaOCl, ZirCleanTM, Ivoclean and KATANATM Cleaner. Tensile bond strength was evaluated for 13 groups (N=10): six cleaning measures against two contaminations (12 experimental groups) and one uncontaminated control group. Scanning electron microscopy was used to observe the control and water-rinsed specimen surfaces. X-ray photoelectron spectroscopy (XPS) was conducted to identify carbon (C1s), nitrogen (N1s), phosphorous (P2p) and zirconium (Zr3d) peaks, from which the elemental ratios C/Zr, N/Zr and P/Zr were calculated. RESULTS: Although water-rinsing removed most of the contaminants from the zirconia surface, bond strength of resin cement was significantly lower compared with the control. Phosphoric acid was ineffective and NaOCl was less reliable in restoring bond strength. The three commercial cleaners (ZirCleanTM, Ivoclean, KATANATM Cleaner) out-performed the other cleaning measures and restored the bond strength of resin cement to zirconia except for the use of ZircleanTM on blood-contaminated surfaces. N/Zr decreased for all cleaned specimens and P/Zr ratio increased for phosphoric acid and KATANATM Cleaner groups. Differences in elemental ratios could indicate different cleaning mechanisms for the zirconia cleaners. CONCLUSION: All three commercial zirconia cleaners are effective in decontaminating saliva-contaminated or blood-contaminated zirconia and increasing the bond strength of resin cement to contaminated zirconia. CLINICAL SIGNIFICANCE: The use of water, phosphoric acid or concentrated sodium hypochorite for cleaning saliva- or blood-contaminated dental zirconia is not recommended. ZirCleanTM works well on decontamination of saliva-contaminated zirconia. Ivoclean or KATANATM Cleaner are useful for decontamination of both saliva- and blood-contaminated zirconia during the intraoral try-in stage to recover the original bond strength of cementation.

Gold-Incorporated Cobalt Phosphide Nanoparticles on Nitrogen-Doped Carbon for Enhanced Hydrogen Evolution Electrocatalysis.

Transition metal phosphides (TMPs) demonstrate great potential for hydrogen evolution reaction (HER) electrocatalysis, but their activities need further improvement. Herein we report a novel Au incorporation strategy to boost the HER catalytic performance of CoP. As a proof of concept, heterostructured Au/CoP nanoparticles dispersed on nitrogen-doped carbon with unique porosity, denoted as Au/CoP@NC-3, are synthesized by thermal treatment of Au-nanoparticle-incorporated ZIF-67 precursor. It shows excellent HER activity as well as good durability in acidic and alkaline condition, respectively, greatly outperforming its Au-free analogue, namely, CoP@NC. In-depth analysis suggests that the improved HER activity of Au/CoP@NC-3 is attributed to the presence of Au nanoparticles which enlarge the electrochemical active surface areas and adjust the electronic structure of active CoP species to enhance the water adsorption and optimize H adsorption for the accelerated HER process.