Alkaline oxygen evolution: exploring synergy between fcc and hcp cobalt nanoparticles entrapped in N-doped graphene

Herein, we report a Mott-Schottky catalyst by entrapping cobalt nanoparticles inside the N-doped graphene shell (Co@NC). The Co@NC delivered excellent oxygen evolution activity with an overpotential of merely 248 mV at a current density of 10 mA cm^–2 with promising long-term stability. The importance of Co encapsulated in NC has further been demonstrated by synthesizing Co nanoparticles without NC shell. The synergy between the hexagonal close-packed (hcp) and face-centered cubic (fcc) Co plays a major role to improve the OER activity, whereas the NC shell optimizes the electronic structure, improves the electron conductivity, and offers a large number of active sites in Co@NC. The density functional theory calculations have revealed that the hcp Co has a dominant role in the surface reaction of electrocatalytic oxygen evolution, whereas the fcc phase induces the built-in electric field at the interfaces with N-doped graphene to accelerate the H⁺ ion transport.     

Effect of oxygen on regulation of properties of moderately boron-doped diamond films

Regulation of oxygen on properties of moderately boron-doped diamond films is fully investigated. Results show that, with adding a small amount of oxygen (oxygen-to-carbon ratio < 5.0%), the crystal quality of diamond is improved, and a suppression effect of residual nitrogen is observed. With increasing ratio of O/C from 2.5% to 20.0%, the hole concentration is firstly increased then reduced. This change of hole concentration is also explained. Moreover, the results of Hall effect measurement with temperatures from 300 K to 825 K show that, with adding a small amount of oxygen, boron and oxygen complex structures (especially B₃O and B₄O) are formed and exhibit as shallow donor in diamond, which results in increase of donor concentration. With further increase of ratio of O/C, the inhibitory behaviors of oxygen on boron leads to decrease of acceptor concentration (the optical emission spectroscopy has shown that it is decreased with ratio of O/C more than 10.0%). This work demonstrates that oxygen-doping induced increasement of the crystalline and surface quality could be restored by the co-doping with oxygen. The technique could achieve boron-doped diamond films with both high quality and acceptable hole concentration, which is applicable to electronic level of usage.     

Noninvasive Temperature Measurement in Dental Materials Using Nd3+, Yb3+ Doped Nanoparticles Emitting in the Near Infrared Region

In this work, the application of near infrared (NIR)-emitting NaYbF₄:1%Tm³⁺@NaLuF₄:30%Nd³⁺ core–shell nanoparticles is reported for noninvasive probing and monitoring the temperature during photopolymerization of dental materials. When excited at 808 nm, the synthesized nanoparticles emit NIR photoluminescence (PL) with two distinctive peaks at 865 and 980 nm which correspond to radiative transitions from the doped Nd³⁺ and Yb³⁺ ions, respectively. Luminescence intensity ratio between these two bands is found to vary with temperature due to temperature-dependent electronic excitation energy transfer between Nd³⁺ and Yb³⁺ ions at the core/shell interface. This finding allows luminescence ratiometric evaluation of the in situ temperature during photopolymerization of resin cement (doped with nanoparticles) in a veneer placement procedure. In addition, the NIR emission also enables PL imaging of the distribution of the adhesive under the veneer. The results highlight that rare-earth ions–doped nanoparticles with both excitation and emission in the NIR spectral range are advantageous for both PL-based nanothermometry and imaging due to the reduced attenuation of NIR light by dental ceramics.     

A Comparative Study of the Semiconductor Behavior of Organic Thin Films: TCNQ-Doped Cobalt Phthalocyanine and Cobalt Octaethylporphyrin

The structure formed by cobalt phthalocyanine (CoPc) and cobalt octaethylporphyrin (CoOEP) with electron-acceptor tetracyano-π-quinodimethane (TCNQ), was studied by Density Functional Theory (DFT) methods. According to theoretical calculations, both cobalt systems can establish dispersion forces related to TCNQ and also in both cases the link between them is built by means of hydrogen bonds. Based on the results of these DFT calculations, we developed experimental work: the organic semiconductors were doped, and the thermal evaporation technique was used to prepare semiconductor thin films of such compounds. The structure of the films was studied by FTIR and Raman spectroscopy. The optical properties of the CoPc-TCNQ and CoOEP-TCNQ films were investigated by means of UV-Vis measurements. The results obtained were used to estimate the type of transitions and the optical bandgap. The results were compared to the previously calculated theoretical bandgap. The CoOEP-TCNQ film presented the smallest theoretical and experimental bandgap. Finally, the electrical properties of the organic semiconductors were evaluated from a PET (polyethylene terephthalate)/indium tin oxide (ITO)/cobalt macrocycle-TCNQ/silver (Ag) device we prepared. The CoOEP-TCNQ-based device showed an ohmic behavior. The device manufactured from CoPc-TCNQ also showed an ohmic behavior at low voltages, but significantly changed to SCLC (space-charge limited conductivity) at high voltage values.     

Facile Synthesis of Mg2+‐Doped Carbon Dots as Novel Biomaterial Inducing Cell Osteoblastic Differentiation

Carbon dots (CDs), as an emerging fluorescent nanomaterial with low toxicity, has been widely applied in various bio‐related fields. However, investigations on their capabilities in guiding osteogenic differentiation are rarely seen, which has great significance in osteoporosis therapy and bone regeneration. Herein, for the first time, a new kind of Mg²⁺‐doped CDs is facilely synthesized through a one‐step hydrothermal method from metal gluconate salts. The CDs can serve as nanocarrier of Mg²⁺ ions entering into cells, and the bioessential metal ions subsequently stimulate osteoblastic differentiation by improving alkaline phosphatase (ALP) activity and upregulation related mRNA expression. Noteworthy, the raw material has almost negligible performance on osteoblastic differentiation compared to Mg‐CDs, which is due to the ultrasmall sizes of CDs and the efficient uptake by cells. Moreover, benefitting from the fluorescence properties, Mg‐CDs can also be applied as cell labeling agents. This work proposes a new strategy to synthesize multifunctional metal ion‐doped CDs, which might had great potential in serving as promising nanodrugs for bone loss therapy.     

A theoretical study on the pure and doped ZnO nanoclusters as effective nanobiosensors for 5-fluorouracil anticancer drug adsorption

The electronic sensitivity and effectiveness of the pristine, Fe,- Mg-, Al- and Ga-doped ZnO nanoclusters interacted with 5-fluorouracil (5-FU) anticancer drug are theoretically investigated in the gas phase using the B3LYP/wB97XD density functional theory calculations with LANL2DZ basis set. It is concluded that 5-FU adsorption on the doped nanoclusters has relatively higher adsorption energy as compared with the pristine zinc oxide. A number of thermodynamic parameters, such as band gap energy (E_g), adsorption energy (E_ad), molecular electrostatic potential, global hardness (η) and density of electronic states, are attained and compared. Also, calculated geometrical parameters and electronic properties for the studied systems indicate that Mg- and Ga-doped Zn₁₂O₁₂ present higher sensitivity to 5-FU compared with the pristine nanocluster. Theoretical results reveal that adsorption of 5-FU on the doped nanoclusters is influenced by the electronic conductance of the nanocluster. Therefore, Mg- and Ga-doped ZnO can be considered as promising nanobiosensors for detection of 5-FU in medicine.     

Construction of Charring-Functional Polyheptanazine towards Improvements in Flame Retardants of Polyurethane

Nitrogen-containing flame retardants have been extensively applied due to their low toxicity and smoke-suppression properties; however, their poor charring ability restricts their applications. Herein, a representative nitrogen-containing flame retardant, polyheptanazine, was investigated. Two novel, cost-effective phosphorus-doped polyheptazine (PCN) and cobalt-anchored PCN (Co@PCN) flame retardants were synthesized via a thermal condensation method. The X-ray photoelectron spectroscopy (XPS) results indicated effective doping of P into triazine. Then, flame-retardant particles were introduced into thermoplastic polyurethane (TPU) using a melt-blending approach. The introduction of 3 wt% PCN and Co@PCN could remarkably suppress peak heat release rate (pHRR) (48.5% and 40.0%), peak smoke production rate (pSPR) (25.5% and 21.8%), and increasing residues (10.18 wt%→17.04 wt% and 14.08 wt%). Improvements in charring stability and flame retardancy were ascribed to the formation of P–N bonds and P=N bonds in triazine rings, which promoted the retention of P in the condensed phase, which produced additional high-quality residues.     

Fe掺杂α-Bi2O3光电性质的第一性原理研究

采用第一性原理杂化泛函HSE06方法对Fe掺杂α-Bi₂O₃的电子结构和光学性质进行了计算研究。结果表明,Fe掺杂α-Bi₂O₃体系有较小的结构变形,本征α-Bi₂O₃的禁带宽度为2.69 eV,Fe掺杂使α-Bi₂O₃的禁带宽度减小(约为2.34 eV)。对其光学性质研究得出Fe掺杂扩展了α-Bi₂O₃对可见光的吸收范围,即发生了红移,从而为Fe掺杂α-Bi₂O₃在光催化领域中的应用提供了理论依据。     

Easy conversion of nitrogen‐rich silk cocoon biomass to magnetic nitrogen‐doped carbon nanomaterial for supporting of Palladium and its application

In this study, magnetic nitrogen‐doped carbon (MNC) was fabricated through facile carbonization and activation of natural silk cocoons containing nitrogen and then combined with Fe₃O₄ nanoparticles to create a good support material for palladium. Palladium immobilization on the support resulted in the formation of magnetic nitrogen‐doped carbon‐Pd (MNC‐Pd). The prepared heterogeneous catalyst was well characterized using FT‐IR, TGA, EDX, FE‐SEM, XRD, VSM, and ICP‐OES techniques. Thereafter, the synthesis of biaryl compounds was conducted to investigate the catalyst performance via the reaction of aryl halides and phenylboronic acid. Further, the catalyst could be used and recycled for six consecutive runs without any significant loss in its activity.     

Solvothermal modification of graphitic C3N4 with Ni and Co phthalocyanines: Structural,optoelectronic and surface properties

Nanocomposites for photocatalytic applications were obtained by alchothermal modification of g-C₃N₄ with cobalt(ii) and nickel(ii) phthalocyanine complexes. The nanocomposites demonstrated higher photocatalytic activity than the bare matrix and stability under actinic irradiation. In the optoelectronic structure of the composites, the E_g value of the g-C₃N₄ matrix increased to 3.05 eV, while for MPc agents, it decreased from 1.96 to 1.82 eV.