Triple Regulations via Fe Redox Boosting Nitrate Reduction to Ammonia at Industrial Current Densities.

Electrochemical nitrate reduction reaction (NO3-RR) has promising prospects for green synthesis of ammonia and environmental remediation. However, the performance of catalysts at high current density usually suffers from the high energy barrier for the nitrate (NO3-) to nitrite (NO2-) and the competitive hydrogen evolution. Herein, we proposed a two-step relay mechanism through spontaneous redox reaction followed electrochemical reaction by introducing low-valence Fe species into Ni2P nanosheets to significantly enhance the NO3-RR performance at industrial current density. The existence of low-valence Fe species bypasses the NO3- to NO2- step through the spontaneous redox with NO3- to produce NO2- and Fe2O3, regulates the electronic structure of Ni2P to reduce the barrier of NO2- to NH3, thirdly prohibits the hydrogen evolution by consuming the excess active hydrogen through reduction of Fe2O3 to recover low-valence Fe species. The triple regulations via Fe redox during the two-step relay reactions guarantee the Fe-Ni2P@NF high ammonia yield of 120.1 mg h-1 cm-2 with Faraday efficiency of more than 90% over a wide potential window and a long-term stability of more than 130 h at ~1000 mA cm-2. This work provides a new strategy to realize the design and synthesis of nitrate reduction electrocatalysts at high current densities.

Auto-optimizing Hydrogen Evolution Catalytic Activity of ReS2 through Intrinsic Charge Engineering.

Optimizing active electronic states responding to catalysis is of paramount importance for developing high-activity catalysts because thermodynamics itself may not favor forming an optimal electronic state. Setting the monolayer transition metal dichalcogenide (TMD) ReS2 as a model for the hydrogen evolution reaction (HER), we uncover that intrinsic charge engineering has an auto-optimizing effect on enhancing catalytic activity through regulating active electronic states. The experimental and theoretical results show that intrinsic charge compensation from S to Re-Re bonds could manipulate the active electronic states, allowing hydrogen to absorb the active sites neither strongly nor weakly. Two types of S sites exhibit the optimal hydrogen adsorption free energies (Δ GH*) of 0.016 and 0.061 eV, which are the closest to zero corresponding to the highest HER activity. This auto-optimization via charge engineering is further demonstrated by higher turnover frequency per sulfur atom of 1-10 s-1 and lower overpotential of -147 mV at 10 mA cm-2 than those of other TMDs through multiscale activation and optimization. This work opens an avenue in designing extensive active catalysts through intrinsic charge engineering strategy.

Oxidative stress-mediated selective antimicrobial ability of nano-VO2 against Gram-positive bacteria for environmental and biomedical applications.

Vanadium dioxide (VO2) is a unique thermochromic material as a result of its semiconductor-metal transition, holding great promise for energy-saving intelligent windows. Herein, pure nano-VO2 from discrete nanoparticles to continuous films were successfully deposited on quartz glass by controlling the sputtering parameters. It was demonstrated that, for Gram-positive S. aureus and S. epidermidis, the nano-VO2 could effectively disrupt bacteria morphology and membrane integrity, and eventually cause death. By contrast, the nano-VO2 did not exhibit significant toxicity towards Gram-negative E. coli and P. aeruginosa. To our knowledge, this is the first report on a selective antimicrobial effect of nano-VO2 materials on Gram-positive bacteria. Based on the experimental results, a plausible mechanism was proposed for the antimicrobial selectivity, which might originate from the different sensitivity of Gram-positive and Gram-negative bacteria to intracellular reactive oxygen species (ROS) level. Elevated intracellular ROS levels exceed the threshold that bacteria can self-regulate to maintain cellular redox homeostasis and thus cause oxidative stress, which can be alleviated by the intervention of glutathione (GSH) antioxidant. In addition, nano-VO2 did not produce significant cytotoxicity (hemolysis) against human erythrocytes within 12 h. Meanwhile, potential cytotoxicity against HIBEpiC revealed a time- and dose-dependent behavior that might be controlled and balanced by careful design. The findings in the present work may contribute to understanding the antimicrobial behavior of nano-VO2, and to expanding the new applications of VO2-based nanomaterials in environmental and biomedical fields.

Efficient adsorption and photocatalytic degradation of Congo red onto hydrothermally synthesized NiS nanoparticles.

NiS nanoparticles (NiS NPs) have been hydrothermally prepared and characterized by the methods of X-ray diffraction, scanning electronic microscope, X-ray photoelectron spectroscopy, UV-Vis diffuse reflectance spectra, photoluminescence, and thermogravimetric analysis. NiS NPs exhibit fast adsorption in the removal of Congo red (CR) in aqueous solution, in which the pseudo-second-order model was the best to describe the adsorption kinetics, and the intraparticle diffusion was not only the rate-limiting step. The NiS NPs also exhibit efficient photocatalytic activity in the degradation of CR under visible-light irradiation, in which the 30 mg/L CR was almost completely degraded after illumination during 210 min. The •OH radicals in the process of photocatalytic degradation were observed by fluorescence technique.

[Quantitative surface analysis of Pt-Co, Cu-Au and Cu-Ag alloy films by XPS and AES].

In order to improve the quantitative analysis accuracy of AES, We associated XPS with AES and studied the method to reduce the error of AES quantitative analysis, selected Pt-Co, Cu-Au and Cu-Ag binary alloy thin-films as the samples, used XPS to correct AES quantitative analysis results by changing the auger sensitivity factors to make their quantitative analysis results more similar. Then we verified the accuracy of the quantitative analysis of AES when using the revised sensitivity factors by other samples with different composition ratio, and the results showed that the corrected relative sensitivity factors can reduce the error in quantitative analysis of AES to less than 10%. Peak defining is difficult in the form of the integral spectrum of AES analysis since choosing the starting point and ending point when determining the characteristic auger peak intensity area with great uncertainty, and to make analysis easier, we also processed data in the form of the differential spectrum, made quantitative analysis on the basis of peak to peak height instead of peak area, corrected the relative sensitivity factors, and verified the accuracy of quantitative analysis by the other samples with different composition ratio. The result showed that the analytical error in quantitative analysis of AES reduced to less than 9%. It showed that the accuracy of AES quantitative analysis can be highly improved by the way of associating XPS with AES to correct the auger sensitivity factors since the matrix effects are taken into account. Good consistency was presented, proving the feasibility of this method.

The effect of powder properties on sintering, microstructure, mechanical strength and degradability of beta-tricalcium phosphate/calcium silicate composite bioceramics.

The effect of powder properties on sintering, microstructure, mechanical strength and degradability of beta-tricalcium phosphate/calcium silicate (beta-Ca3(PO4)2/CaSiO3, beta-TCP/CS) composite bioceramics was investigated. beta-TCP/CS composite powders with a weight ratio of 50:50 were prepared by three different methods: mechanical milling method (TW-A), two-step chemical precipitation method (TW-B) and in situ chemical co-precipitation method (TW-C), and then the three composite powders were uniaxially compacted at 30 MPa, followed by cold isostatic pressing into rectangular-prism-shaped specimens under a pressure of 200 MPa for 15 min, and then sintered at 1150 degrees C for 5 h. The TW-B powders with less agglomerative morphologies and uniform nano-size particles attained 96.14% relative density (RD). A uniform microstructure with about 120 nm grains was observed. Whereas, the samples obtained from TW-A and TW-C powders only reached a RD of 63.08% and 78.86%, respectively. The bending strength of the samples fabricated from TW-B reached 125 MPa, which was more than 3.7 and 1.5 times higher as compared with that of samples obtained from TW-A and TW-C powders, respectively. Furthermore, the degradability of the samples fabricated from TW-B powders was obviously lower than that of the samples fabricated from TW-A and TW-C powders.

[Mineralogical effect correction for pressed iron ore samples in wavelength dispersive X-ray fluorescence analysis].

The possibility of correcting mineralogical effect for pressed powder pellets of iron ore samples was studied in wavelength dispersive X-ray fluorescence analysis of major and minor elements with 10 Chinese iron ore CRMs. Two methods were applied to reduce the influence of mineralogical effect. The first one is to check 20 angles for every sample before measurement to correct peak shift; another method is replacing peak intensity with peak area of the analytical line to correct the shape distortion of the spectrum. The K factors of the two methods for each element were compared to those from regular measurements. The results show that the calibration for most of the elements was improved, although to different degrees. The improvement in the calibration for sulfur is evident. The calibration for other elements can meet the general requirements except for total iron.

[Calculation of the contributions of scattering effects to the X-ray fluorescence intensities].

The contribution of scattering effects to the X-ray fluorescence intensity was studied for pure element samples, BaB binary samples and fused disk samples by theoretic calculation and experiment. Three scattering effects were considered in the present study, i. e. coherent scattering effect, incoherent scattering effect, and primary fluorescence that was scattered into the direction of detector. The study shows that the contribution of scattering effects to the intensity of fluorescence is related to the energy of the atomic absorption edge, and the sample's matrix. The higher the energy of the atomic absorption edge, the more the contribution of scattering effects to the intensity of fluorescence. The contribution of scattering effects to the fluorescence intensity is larger for light matrix samples than heavy matrix samples. The results of experiment show that the accuracy of theoretic calculation was evidently improved when the scattering effects were considered in the theoretic calculation for the intensity of fluorescence.

[Study on the influence of excitation voltage and anode on the contribution of scattering effects to the intensity of X-ray fluorescence].

The influence of X-ray tube spectral distribution related to the X-ray tube voltage and target anode on the contribution of scattering effects to the intensity of fluorescence was studied by using some fused disk samples. Three scattering effects were considered. They are coherent scattering effect, incoherent scattering effect and primary fluorescence scattered into the direction of detector respectively. For the fused beads under investigation, the results show that the contributions of coherent scattering effect and the primary fluorescence scattered into the direction of detector decreased with increasing the tube voltage, and the contribution was larger when excited by the X-ray from Cr target than that from Rh target. On the contrary, the contribution of incoherent scattering effect to the intensity of fluorescence increased with increasing the voltage, and was larger when excited by the X-ray from Rh target than that from Cr target. The sum of the contribution of scattering effects to the intensity of fluorescence increased with increasing the voltage, and was larger when excited by the X-ray from Rh target than that from Cr target.