Designing Efficient Non-Precious Metal Electrocatalysts for High-Performance Hydrogen Production: A Comprehensive Evaluation Strategy.

Developing abundant Earth-element and high-efficient electrocatalysts for hydrogen production is crucial in effectively reducing the cost of green hydrogen production. Herein, a strategy by comprehensively considering the computational chemical indicators for H* adsorption/desorption and dehydrogenation kinetics to evaluate the hydrogen evolution performance of electrocatalysts is proposed. Guided by the proposed strategy, a series of catalysts are constructed through a dual transition metal doping strategy. Density Functional Theory (DFT) calculations and experimental chemistry demonstrate that cobalt-vanadium co-doped Ni3N is an exceptionally ideal catalyst for hydrogen production from electrolyzed alkaline water. Specifically, Co,V-Ni3N requires only 10 and 41 mV in alkaline electrolytes and alkaline seawater, respectively, to achieve a hydrogen evolution current density of 10 mA cm-2. Moreover, it can operate steadily at a large industrial current density of 500 mA cm-2 for extended periods. Importantly, this evaluation strategy is extended to single-metal-doped Ni3N and found that it still exhibits significant universality. This study not only presents an efficient non-precious metal-based electrocatalyst for water/seawater electrolysis but also provides a significant strategy for the design of high-performance catalysts of electrolyzed water.

Improved Cell Properties of Human Dental Pulp Stem Cells (hDPSCs) Isolated and Expanded in a GMP Compliant and Xenogeneic Serum-free Medium.

BACKGROUND/AIM: Human dental pulp mesenchymal stem cells (hDPSCs) are considered to be a good cell source for cell-based clinical therapy, due to the advantages of high proliferation capacity, multilineage differentiation potential, immune regulation abilities, less ethnic concerns and non-invasive access. However, hDPSCs were traditionally isolated and expanded in medium containing fetal bovine serum (FBS), which is a barrier for clinical application due to the safety issues (virus transmission and allergy). Although many studies make efforts to screen out a suitable culture medium, the results are not promising so far. Therefore, a standard good manufacturing practice (GMP) compliant culture system is urgently required for the large-scale cell production. This study aimed to find suitable culture conditions for producing clinical grade hDPSCs to meet the requirements for clinical cell-based therapy and further to promote the application of hDPSCs into tissue regeneration or disease cure. MATERIALS AND METHODS: We derived hDPSCs from nine orthodontic teeth expanded in two different media: a GMP compliant and xenogeneic serum-free medium (AMMS) and a serum containing medium (SCM). Cell propterties including morphology, proliferation, marker expression, differentiation, stemness, senescence and cytokine secretion between these two media were systematically compared. RESULTS: hDPSCs cultured in both media exhibited the typical characteristics of mesenchymal stem cells (MSCs). However, we found that more cell colonies formed in the primary culture in AMMS, and the hDPSCs displayed higher proliferation capacity, differentiation potential and better stemness maintenance during sub-culturing in AMMS. CONCLUSION: Cell properties of hDPSCs could be improved when they were isolated and expanded in AMMS, which might provide a good candidate of culture medium for large-scale cell manufacturing.

Collaborative Interface Optimization Strategy Guided Ultrafine RuCo and MXene Heterostructure Electrocatalysts for Efficient Overall Water Splitting.

Developing highly active and robust electrocatalysts for the hydrogen/oxygen evolution reaction (HER/OER) is crucial for the large-scale utilization of green hydrogen. In this study, a collaborative interface optimization guided strategy was employed to prepare a metal-organic framework (MOF) derived heterostructure electrocatalyst (MXene@RuCo NPs). The obtained electrocatalyst requires overpotentials of only 20 mV for the HER and 253 mV for the OER to deliver a current density of 10 mA/cm2 in alkaline media, respectively, and it also exhibits great performance at high current density. Experiments and theoretical calculations reveal that the doped Ru introduces second active sites and decreases the diameter of nanoparticles, which greatly enhances the number of active sites. More importantly, the MXene/RuCo NPs heterogeneous interfaces in the catalysts exhibit great synergistic effects, decreasing the work function of the catalyst and improving the charge transfer rate, thus reducing the energy barrier of the catalytic reaction. This work represents a promising strategy for the development of MOF-derived highly active catalysts to achieve efficient energy conversion in industrial applications.

Thermodynamic properties study of polyoxometalate Na7[H2PV14O42].

Lithium-ion batteries (LIBs) are widely used in electronic applications because of their high voltage, high specific energy, long lifespan, and other characteristics. Electrode materials have garnered interest as an indispensable component of LIBs. Na7[H2PV14O42] is used as an electrode material because of its excellent properties. In this study, Na7[H2PV14O42] was synthesized by the water bath method using NaVO3 as the raw material, experimentally characterized, and its thermodynamic data were measured using the Neumann-Kopp rule from 298.15 to 843 K, a Physical Property Measurement System from 15 to 309 K, and the MHTC 96 line from 473 to 773 K. The data were fitted to the Debye-Einstein heat capacity equation at low temperatures and a polynomial function at higher temperatures. The heat capacity equation of Na7[H2PV14O42] was obtained from the fitted curves. The corresponding enthalpy (▵298.15 THm), entropy (▵298.15 TSm), and Gibbs energy (▵298.15 TGm) (from 298.15 to 800 K) were calculated according to the heat capacity equation. The obtained heat capacity of Na7[H2PV14O42], as a function of temperature, was modeled as Cp = 1502.30 + 0.27T - 2.44E7T-2 J mol-1 K-1 (473-773 K). This study can compensate for the thermodynamic deficiency of Na7[H2PV14O42].

Selective nitridation-corrosion process to recover vanadium, titanium, chromium, and iron from vanadium slag.

Vanadium slag (V-slag) is an important secondary V source, but other valuable elements are discarded in the tailings in industry. Herein, a green nitridation-corrosion process is proposed for the comprehensive recovery of valuable elements (V, Ti, Cr, Fe) from V-slag without producing hazardous waste. Thermodynamic results indicate that ammonia gas (NH3) can selectively reduce Fe and nitride V, Cr, and Ti. The main phase composition of the nitrided V-slag included metallic Fe, nitrides, and diopside under optimal conditions, and their relative contents were 42.5, 26.2, and 31.3%, respectively, after roasting at 1000 °C for 6 h. The effects of the main parameters on corrosion test were investigated, and the highest weight-gain ratio attained was 19.6%. FeOOH crystallizes on the surface of the nitrided V-slag due to the oxidization of metallic Fe. The phase evolution during the entire process is spinel/olivine/diopside → Fe/nitrides/diopside → FeOOH/nitrides/diopside. Owing to finer particle sizes, most FeOOH is separated by wet sieving (<1400 mesh). The purity of the enriched nitrides attained was 43% after pickling to remove excess Fe. The total recovery rates of Fe, V, Ti, Cr were 87.76%, 95.92%, 92.92%, 92.11%, respectively. This paper provides a sustainable strategy for the comprehensive utilization of V-slag, and guides the cleaner treatment of other similar minerals.

Bonding Heterogeneity Leads to Hierarchical and Ultralow Lattice Thermal Conductivity in Sodium Metavanadate.

Sodium metavanadate (NaVO3) is a promising low-cost candidate as a cathode material for sodium-ion batteries (SIBs) owing to its high cycle performance. Its thermal transport, although being a central factor limiting its practical applications, remains scarce. Herein, we comprehensively investigate the intrinsic thermal transport properties of the two phases of NaVO3 using the unified theory. Importantly, we identify a hierarchical thermal transport mechanism in NaVO3 and the significant contribution of diffusive thermal transport. With the combined two channels, we reveal that NaVO3 has the anisotropic and ultralow thermal conductivity κ, which is derived from the bonding heterogeneity with the coexistence of strong V-O bonds and weak Na-O bonds, implying the possibility of engineering the κ of SIBs by spatially tuning the sodium concentration distribution. Our work establishes a fundamental understanding of the intrinsic thermal transport of NaVO3 and provides guidance toward designing tunable thermal conductivity cathode materials for SIBs.

Comprehensive Study of Electronic, Optical, and Thermophysical Properties of Metavanadates CaV2O6 and MgV2O6.

Calcium metavanadate (CaV2O6) and magnesium metavanadate (MgV2O6) have received considerable attention due to their great potential for many practical applications; however, a fundamental understanding of their intrinsic physical properties is still not well established. Here, we present a comprehensive experimental and theoretical study of the optical, electronic, and lattice dynamic properties of CaV2O6 and MgV2O6. We find that both compounds are semiconductors with indirect band gaps and exhibit visible light-emitting properties, which are thus expected to be the ideal candidates for phosphors or optoelectronic devices. Through density functional theory (DFT) calculations, we further show that CaV2O6 exhibits negative thermal expansion (NTE) below 80 K due to the flexible or intense coupled rocking of the CaO6 octahedra. Moreover, using the dual-phonon model, we disclose the hierarchical thermal transport features of these two compounds, in which diffusive channels make a significant contribution to the thermal conductivity κ, resulting in the weak temperature dependence of κ deviating from the typical κ ∼T-1 given by the phonon gas model. With the consideration of normal and diffusive phonons, we predict the ultralow and large anisotropic thermal conductivities of CaV2O6 and MgV2O6. This work provides a fundamental understanding of the optical, electronic, and thermal properties of metal-ion-intercalated layered vanadium oxides, which may promote the functional applications of metavanadates.

The role of metabolites under the influence of genes and lifestyles in bone density changes.

Purpose: Osteoporosis is a complex bone disease influenced by numerous factors. Previous studies have found that some metabolites are related to bone mineral density (BMD). However, the associations between metabolites and BMD under the influence of genes and lifestyle have not been fully investigated. Methods: We analyzed the effect of metabolites on BMD under the synergistic effect of genes and lifestyle, using the data of 797 participants aged 55-65 years from the Taizhou Imaging Study. The cumulative sum method was used to calculate the polygenic risk score of SNPs, and the healthful plant-based diet index was used to summarize food intake. The effect of metabolites on BMD changes under the influence of genes and lifestyle was analyzed through interaction analysis and mediation analysis. Results: Nineteen metabolites were found significantly different in the osteoporosis, osteopenia, and normal BMD groups. We found two high-density lipoprotein (HDL) subfractions were positively associated with osteopenia, and six very-low-density lipoprotein subfractions were negatively associated with osteopenia or osteoporosis, after adjusting for lifestyles and genetic factors. Tea drinking habits, alcohol consumption, smoking, and polygenic risk score changed BMD by affecting metabolites. Conclusion: With the increased level of HDL subfractions, the risk of bone loss in the population will increase; the risk of bone loss decreases with the increased level of very-low-density lipoprotein subfractions. Genetic factors and lifestyles can modify the effects of metabolites on BMD. Our results show evidence for the precise prevention of osteoporosis.

Pyrolysis Behavior of Pyrite under a CO-H2 Atmosphere.

The transformation behavior of pyrite (FeS2) in the blast furnace process is critical to control the formation and emission of gaseous sulfides in the top gas of ironmaking but has seldom been explored. In present work, the pyrolysis of pyrite from 200 to 900 °C under a CO-H2 atmosphere was investigated by thermal-gravimetric and mass spectrometry. The thermodynamic theoretical calculations were carried out to further understand the transformation process. The results show that FeS2 is almost completely reduced to FeS under various CO-H2 atmospheres. H2S and carbonyl sulfide (COS) are the main gaseous sulfides formed through the pyrolysis reactions of FeS2 under a CO-H2 atmosphere. A higher H2 concentration can reduce the pyrolysis reaction temperature of FeS2, which is favorable for the conversion of sulfides to H2S, while a higher CO concentration promotes the conversion of sulfides to COS. Besides, the pyrolysis products of FeS2 by order from the former to latter under a strong reductive atmosphere (CO-H2) with increasing temperature are as follows: COS → S → H2S → S2 → CS2.

Homogeneous and well-aligned GaN nanowire arrays via a modified HVPE process and their cathodoluminescence properties.

In this work, we demonstrate the growth of homogeneous and well-aligned [0001]-oriented 1-D GaN nanoarrays via a modified hydride vapor phase epitaxy (HVPE) process using GaCl3 and NH3 as precursors. The density and length of the grown nanowires can be easily controlled by the process parameters. It was found that the growth technique provides Cl-rich growth conditions, which lead to special morphology and optical properties of the GaN nanoarrays. Different from reported GaN nanowires, the as-synthesized GaN nanoarrays in this study exhibit a hollow bamboo-like structure. Also, the cathodoluminescence spectrum shows strong visible luminescence between 400 and 600 nm wavelengths centered at 450 nm, and the disappearance of an intrinsic emission peak, which has been investigated in detail with the assistance of first-principles calculations. The strategy proposed in this work will pave a solid way for the controlled nucleation and growth of well-aligned GaN nanowire arrays which are significant for applications in large-scale integrated optoelectronic nanodevices, functionalized sensors and photoelectrocatalysis.

Tuning the Electronic Structure of the CoP/Ni2P Nanostructure by Nitrogen Doping for an Efficient Hydrogen Evolution Reaction in Alkaline Media.

As one of the most sustainable, efficient, and cleanest ways for hydrogen production, electrochemical water splitting relies heavily on cost-efficient and stable electrocatalysts. Herein, a self-supported and nitrogen-doped hybrid CoP/Ni2P was synthesized through a simple two-step hydrothermal process followed by low-temperature phosphorization and nitridation (N-CoP/Ni2P@NF). Both experimental and density functional theory calculation results suggest that nitrogen doping can tune the electrical structure of the CoP/Ni2P heterostructure and thus optimize the free energy of adsorbed H on the surface of N-CoP/Ni2P@NF and accelerate the electronic transport activity. The prepared N-CoP/Ni2P@NF exhibits excellent electrocatalytic hydrogen evolution reaction (HER) performance, which merely requires an overpotential of -46 mV at -10 mA cm-2 and shows a negligible decay after a long durability test for 72 h in alkaline (1.0 M KOH) media. Consequently, this work supplies a novel strategy with great potential for designing transition metal phosphate-based catalysts with high HER performance.

Photoluminescence and optical temperature sensing properties of Dy3+-doped Na0.5Bi0.5TiO3 multifunctional ferroelectric ceramics.

A series of Dy3+ doped Na0.5Bi0.5TiO3 (NBT: xDy3+, x = 0.003-0.018) lead-free ferroelectric ceramics were successfully prepared by a solid-state reaction method. The Dy3+ ions composition dependent photoluminescence properties were systematically studied. All the samples display intense characteristic emission of Dy3+ under an excitation wavelength of 454 nm, which are attributed to the transitions of 4F9/2 → 6HJ/2 (J = 13, 11 and 9). All the samples show strong orange-yellow emission, which could be applied to warm white light hopefully. When the content of Dy3+ is equal to 0.012, the ceramic has the optimal luminous performance. Remarkable thermal quenching of the luminous intensity ceramic occurs as the temperature is higher than initial temperature 293 K. Furthermore, Dy3+ activated photoluminescence performance combined with the presence of ferroelectricity in the NBT host can be applied to developing non-contact optical temperature sensitive materials and other future novel optoelectronic devices.

A novel recycling approach for efficient extraction of titanium from high-titanium-bearing blast furnace slag.

The recycling of high-titanium-bearing blast furnace slag (TiO2 > 23 wt.%) is an urgent problem that has attracted global research attention. To achieve high-efficiency, low-consumption, clean, and high value-added recycling utilization, a new process is proposed herein, which entails reacting a CH4-H2-N2 gas mixture with the titanium-bearing blast furnace slag to initially produce Ti(C, N, O) at a low temperature, whereafter the product is purified and chlorinated. The effects of Fe2O3, urea, and sawdust on the reduction and carbonitriding characteristics are also investigated. The results indicate that the Fe2O3 additive can promote the formation of Ti(C, N, O), while urea and sawdust are instrumental for enhancing gas diffusion in solid powders. The proposed novel recycling process was assessed and it evinced many advantages and great feasibility.

Microstructure and Mechanical Properties of Graphene Oxide-Reinforced Titanium Matrix Composites Synthesized by Hot-Pressed Sintering.

Ti matrix composites reinforced with 1-5 wt% graphene oxide (GO) were prepared by hot-pressed sintering in argon atmosphere. The effect of sintering temperature on the microstructures and mechanical properties of the composite was also evaluated. The results show that TiC nanoparticles were formed in situ as interfacial products via the reaction between Ti and GO during sintering. With increases in GO content and sintering temperature, the amount of TiC increased, improving the mechanical properties of the composites. GO was also partly retained with a lamellar structure after sintering. The composite reinforced with 5 wt% GO exhibited a hardness of 457 HV, 48.4% higher than that of pure Ti at 1473 K. The Ti-2.5 wt% GO composite sintered at 1473 K achieved a maximum yield stress of 1294 MPa, which was 62.7 % higher than that of pure Ti. Further increasing the GO content to 5 wt% led to a slight decrease in yield stress owing to GO agglomeration. The fracture morphology of the composite reinforced with GO exhibited a quasi-cleavage fracture, whereas that of the pure Ti matrix showed a ductile fracture. The main strengthening mechanism included grain refinement, solution strengthening, and dispersion strengthening of TiC and GO.

Maternal prenatal exposure to environmental factors and risk of childhood acute lymphocytic leukemia: A hospital-based case-control study in China.

OBJECTIVE: To investigate an association between maternal prenatal exposure to several environmental factors and risk of childhood acute lymphocytic leukemia (ALL), and the possible interactions in the Chinese population. METHODS: 345 cases with ALL and their 1:1 age, gender, residence region matched controls aged 0-15 years were recruited from four hospitals in Henan Province from 2014 to 2016. Information was collected by interviews using a questionnaire. Unconditional logistic regression adjusted for age, gender, residence region and relevant confounders was carried out to generate the odds ratios (ORs) and 95% confidence intervals (CIs). RESULTS: Our data indicate that maternal prenatal exposure to interior housing renovation (adjusted OR: 2.98, 95% CI: 1.51-5.86) or pesticides (adjusted OR: 1.48, 95% CI: 1.67-2.28) increased the risk of childhood ALL. Various subgroup analyses stratified by child's gender, age at diagnosis and other factors also supported these results. However, no interaction was detected between exposure to internal housing renovation and pesticides using an additive model. No significant links between maternal exposures to, environmental tobacco smoking (ETS), antipyretic analgesia intake, or viral infectious diseases with risk of ALL were detected. CONCLUSION: Findings in our study are in line with the existing literatures, which support the hypothesis that maternal prenatal exposure to interior housing renovation and pesticides are risk factors for childhood ALL. Notably, we found no interaction between these two risk factors, these findings may inform prevention and early detection strategies.

Segregation and Morphological Evolution of Si Phase during Electromagnetic Directional Solidification of Hypereutectic Al-Si Alloys.

Understanding the Si segregation behavior in hypereutectic Al-Si alloys is important for controlling the micro- and macrostructures of ingots. The macrosegregation mechanism and morphological evolution of the primary Si phase were investigated during electromagnetic directional solidification (EMDS). Both numerical simulations and experimental results strongly suggested that the severe macrosegregation of the primary Si phase was caused by fluid flow and temperature distribution. Microscopic analysis showed that the morphological evolution of the Si crystal occurred as follows: planar → cellular → columnar → dendritic stages during EMDS. Based on constitutional supercooling theory, a predominance area diagram of Si morphology was established, indicating that the morphology could be precisely controlled by adjusting the values of temperature gradient (G), crystal growth rate (R), and solute concentration (C0). The results provide novel insight into controlling the morphologies of primary Si phases in hypereutectic Al-Si alloys and, simultaneously, strengthen our understanding of the macrosegregation mechanism in metallic alloys.

Mineralogical characterisation and magnetic separation of vanadium-bearing converter slag.

The recycling of metallic iron is commonly the first step to fully use the converter slag, which is the biggest waste discharge in the steelmaking process. This study presents a proposed improved process of separating metallic iron from vanadium-bearing converter slag more efficiently. The mineralogical and morphological characteristics of the converter slag were first investigated, and the results showed that most of the iron was incorporated in the spinel and olivine. Grinding, sieving and magnetic separation were combined to recover metallic iron from the converter slag, and yielded approximately 41.5% of iron in which the iron content was as high as 85%, and the non-magnetic concentrate contains 8.56% vanadium with a yield of 95.3% and 8.63% titanium with a yield of 85.3%. The magnetic part can be used as the raw materials in the steel making process, whereas the non-magnetic part can be used as the raw materials for the further extraction of vanadium.

Recovery of tailings from the vanadium extraction process by carbothermic reduction method: Thermodynamic, experimental and hazardous potential assessment.

A cleaner process is tremendously required to deal with the vanadium tailings, which may cause serious environmental problem due to the high content of water soluble hazardous elements such as V and Cr. This problem can be possibly solved by proposed high temperature reduction-magnetic separation process, in which, V, Cr and Fe can be recycled as ferroalloy. The thermodynamic calculation results reveal that a higher temperature (>1127.8 °C) promotes the reduction of Fe, V and Cr, and improves the recovery rates of V and Cr in liquid iron. The reduction behavior of vanadium tailings was investigated using XRD, TG/DSC, SEM, EDS and ICP-OES techniques. The EDS results show that a small portion of V was remained in the slag phase when roasted at 1300 °C, while nearly all of V and Cr can concentrate in ferroalloy at 1400 °C. Approximatly 90% of V and 95% of Cr recovery in magnetic fraction can be obtained for the magnetic separation step. A small portion of V and Cr is remained in the non-magnetic final tailings, however, the hazardous potential assessments results indicate that such kind of tailings can safely use as secondary materials or stockpiled as an end-waste.

Improving the property of calcium ferrite using a sonochemical method.

Power ultrasonic vibration was applied to the solidification of calcium ferrite (CF) melt in this study. The results indicated that power ultrasound can promote the formation of CF by accelerating the solidification process. Ultrasonic vibration greatly refined the CF grains, resulting the grain size decreased from 1893 to 437 µm. Meanwhile, ultrasonic vibration significantly enhanced the compressive strength, reduced the reduction time and improved the reducibility of CF slags. With ultrasonic treatment, the ultimate compressive strength of samples increased from 37.5 to 67.8 MPa, and the reduction time decreased from 225 to 136 min.

Effect of ultrasonic vibration treatment on solid-state reactions between Fe2O3 and CaO.

In the present study, ultrasonic vibration was applied to the solid-state reaction between Fe2O3 and CaO. The effect of the ultrasonic vibration treatment on the formation of CaFe2O4 (CF) from the solid-state reaction was investigated by X-ray diffraction (XRD) and the Rietveld structure refinement method. The results indicated that the solid-state reaction between Fe2O3 and CaO was accelerated by ultrasonic treatment (UT), which efficiently lowered the formation temperature of the solid-state CF and increased the quantity formed by enhancing the mass transfer process of the reactions. Without the UT, CF and Ca2Fe2O5 (C2F) were produced at 750°C and the mass fractions of CF and C2F increased with the experiment temperature, with approximately 47.76% CF and 40.66% C2F produced at 850°C. With the UT, mass fractions of 5.67% CF and 18.20% C2F were formed at 700°C, and increasing the experiment temperature enhanced the formation of CF and C2F. Moreover, a significantly greater amount of CF than C2F was formed when the temperature exceeded 700°C. A CF mass fraction of approximately 98.73% was obtained by UT at 850°C, much higher than the 47.76% obtained without UT. In addition, increasing the ultrasonic power influenced the formation of the CF phase. The CF content increased from 19% to 77.34% with increasing ultrasonic power from 0 to 89%×2kW. Furthermore, a prolonged UT time also promoted the formation of solid phase CF. The mass fraction of CF ranged from 19% to 77.34% when the UT time was varied from 0 to 150min.