Efficient overall water splitting over a Mo(IV)-doped Co3O4/NC electrocatalyst

To meet the demand of producing hydrogen at low cost, a molybdenum (Mo)-doped cobalt oxide (Co₃O₄) supported on nitrogen (N)-doped carbon (x%Mo–Co₃O₄/NC, where x% represents Mo/Co molar ratio) is developed as an efficient bifunctional electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). This defect engineering strategy is realized by a facile urea oxidation method in nitrogen atmosphere. Through X-ray diffraction (XRD) refinement and other detailed characterizations, molybdenum ion (Mo⁴⁺) is found to be doped into Co₃O₄ by substituting cobalt ion (Co²⁺) at tetrahedron site, while N is doped into carbon matrix simultaneously. 4%Mo–Co₃O₄/NC is the optimized sample to show the lowest overpotentials of 91 and 276 mV to deliver 10 mA cm^?2 for HER and OER in 1 M potassium hydroxide solution (KOH), respectively. The overall water splitting cell 4%Mo–Co₃O₄/NC||4%Mo–Co₃O₄/NC displays a voltage of 1.62 V to deliver 10 mA cm^?2 in 1 M KOH. The Mo⁴⁺ dopant modulates the electronic structure of active cobalt ion (Co³⁺) and boosts the water dissociation process during HER, while the increased amount of lattice oxygen and formation of pyridinic nitrogen due to Mo doping benefits the OER activity. Besides, the smaller grain size owing to Mo doping leads to higher electrochemically active surface area (ECSA) on 4%Mo–Co₃O₄/NC, resulting in its superior bifunctional catalytic activity.     

Improved rheological properties and stability of multiwalled carbon nanotubes/polymer in harsh environment

This work aims to improve the rheological properties and stability of multiwalled carbon nanotubes (MWCNTs)/acrylamide (AA) base skeleton polymer blends at harsh environment of high salinity-high temperature (HS-HT) or various pH. Different co/terpolymers have been accomplished to modify the structure of AA polymer by free-radical copolymerization of AA-based monomers. Anionic, cationic, and hydrophobic functional groups were used for the synthesis of polyelectrolyte, polyampholytic, and partially hydrophobic AA polymer types. The conversion, molecular weight, and poly dispersity of co/terpolymers have been evaluated by nuclear magnetic resonance (¹H-NMR), gel permeation chromatography, and differential scanning calorimetry analysis. The effects of sonication power, concentration of polymer, and concentration of MWCNTs were also investigated on rheological behavior of co/terpolymers. The results show that negative polyelectrolyte and polyampholytic polymers are the best candidates for the improvement of MWCNTs/polymer stability and viscosity at HS-HT and alkali environment, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47205.     

Preparation of PEDOT-modified double-layered hollow carbon spheres as Pt catalyst support for methanol oxidation

In this paper, Pt nanoparticles (Pt NPs) deposited hybrid carbon support is prepared by modifying double-layered hollow carbon spheres（DLHCs）with poly(3,4-ethylenedioxythiophene) (PEDOT) and used as anode catalyst of methanol oxidation. The structure of nanocomposites is characterized by SEM, TEM, FT-IR, XRD and XPS, confirming the greatly enhanced synergistic effect between the PEDOT and DLHCs, and illustrating the uniform distribution of Pt NPs on the PEDOT/DLHCs composite surface with a small particle size (~2.63 nm). Cyclic voltammetry, chronoamperometry and impedance spectroscopy applied to determine the electrocatalytic activity of catalysts, it is found that the synthesized PEDOT/DLHCs/Pt possesses excellent characteristics such as large electrochemically active surface area and high mass activity of 59.45 m² g⁻¹ and 807 mA mg⁻¹ in 0.5 M H₂SO₄ containing 1 M methanol solution, which is almost 1.24 and 2.8 times greater than those of commercial Pt/C, and the catalyst exhibits superior stability after 500 durability cycles. The enhanced electrocatalytic behavior can be ascribed to the excellent electronic conductivity of PEDOT-modified DLHCs and the strong binding of PEDOT/DLHCs to Pt NPs, suggesting that the PEDOT/DLHCs/Pt is a promising electrocatalyst for direct methanol fuel cell.     

Dual functions of three-dimensional hierarchical architecture on improving the rate capability and cycle performance of LiNi0.8Co0.1Mn0.1O2 cathode material for lithium-ion battery

The main obstacles in lithium-ion battery are limited by rate performance and the rapid capacity fading of LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811). Herein, a novel three-dimensional (3D) hierarchical coating material has been fabricated by in situ growing carbon nanotubes (CNTs) on the surfaces of Ni–Al double oxide (Ni–Al-LDO) sheets (named as LDO&CNT) with Ni–Al double hydroxide (Ni–Al-LDH) as both the substrate and catalyst precursor. The resultant LDO&CNT nanocomposites are uniformly coated on the surfaces of NCM811 by the physical mixing method. The rate capability of the resultant cathode material retains to 78.80% at a current rate of 3C. Its capacity retention increases by 6.7–14.42% compared with pristine NCM811 after 100 cycles within a potential range of 2.75–4.3 V at 0.5C. The improved rate capability and cycle performance of NCM811 are assigned to the synergistic effects between Ni–Al-LDO and CNTs. The hierarchical LDO&CNT nanocomposites coating on the surface of NCM811 avoids the aggregation of conductive CNTs and the stacking of Ni–Al-LDO nanosheets. Furthermore, it accelerates Li⁺ and electrons shuttle and reduces the reaction of Li₂O with H₂O and CO₂ in air, which results in Li₂CO₃ and LiOH alkali formation on the NCM811 surface.     

Engineering Silver-Enriched Copper Core-Shell Electrocatalysts to Enhance the Production of Ethylene and C2+ Chemicals from Carbon Dioxide at Low Cell Potentials

Copper catalysts are widely studied for the electroreduction of carbon dioxide (CO₂) to value-added hydrocarbon products. Controlling the surface composition of copper nanomaterials may provide the electronic and structural properties necessary for carbon-carbon coupling, thus increasing the Faradaic efficiency (FE) towards ethylene and other multi-carbon (C₂₊) products. Synthesis and catalytic study of silver-coated copper nanoparticles (Cu@Ag NPs) for the reduction of CO₂ are presented. Bimetallic CuAg NPs are typically difficult to produce due to the bulk immiscibility between these two metals. Slow injection of the silver precursor, concentrations of organic capping agents, and gas environment proved critical to control the size and metal distribution of the Cu@Ag NPs. The optimized Cu@Ag electrocatalyst exhibited a very low onset cell potential of −2.25 V for ethylene formation, reaching a FE towards C₂₊ products (FE_C2+) of 43% at −2.50 V, which is 1.0 V lower than a reference Cu catalyst to reach a similar FE_C2+. The high ethylene formation at low potentials is attributed to enhanced C C coupling on the Ag enriched shell of the Cu@Ag electrocatalysts. This study offers a new catalyst design towards increasing the efficiency for the electroreduction of CO₂ to value-added chemicals.     

Studies on waterline corrosion processes and corrosion product characteristics of carbon steel in 3.5 wt% NaCl solution

The waterline corrosion behaviors of carbon steel partially immersed in a 3.5 wt% NaCl solution were investigated using the wire beam electrode technique, and the effects of corrosion products on the processes of waterline corrosion were analyzed. The results demonstrated that the initial stage and development stage of waterline corrosion were mainly controlled by the concentration and diffusion of dissolved oxygen, respectively, and the deceleration stage of waterline corrosion was mainly affected by corrosion products. The main component of the yellow corrosion products was γ-FeOOH, and γ-FeOOH that exhibited a high reduction reactivity could be involved in the cathodic reaction. The black corrosion products were mainly composed of Fe₃O₄ with strong thermodynamic stability and the processes of dissolved oxygen diffusion and ion transports were obviously affected due to the continuous accumulation of Fe₃O₄ on the surface of the electrodes. Polarity reversals were observed on the single electrodes below the waterline, but the reasons for the phenomena were different from each other.     

Strategies to Apply Water-Deficit Stress: Similarities and Disparities at the Whole Plant Metabolism Level in Medicago truncatula

Water-deficit stresses such as drought and salinity are the most important factors limiting crop productivity. Hence, understanding the plant responses to these stresses is key for the improvement of their tolerance and yield. In this study M. truncatula plants were subjected to 250 mM NaCl as well as reduced irrigation (No-W) and 250 g/L polyethylene glycol (PEG)-6000 to induce salinity and drought stress, respectively, provoking a drop to −1.7 MPa in leaf water potential. The whole plant physiology and metabolism was explored by characterizing the stress responses at root, phloem sap and leaf organ level. PEG treatment led to some typical responses of plants to drought stress, but in addition to PEG uptake, an important impairment of nutrient uptake and a different regulation of carbon metabolism could be observed compared to No-W plants. No-W plants showed an important redistribution of antioxidants and assimilates to the root tissue, with a distinctive increase in root proline degradation and alkaline invertase activity. On the contrary, salinity provoked an increase in leaf starch and isocitrate dehydrogenase activity, suggesting key roles in the plant response to this stress. Overall, results suggest higher protection of salt-stressed shoots and non-irrigated roots through different mechanisms, including the regulation of proline and carbon metabolism, while discarding PEG as safe mimicker of drought. This raises the need to understand the effect at the whole plant level of the different strategies employed to apply water-deficit stress.     

Environmental impact estimation of ceramic lightweight aggregates production starting from residues

Within a circular economy approach, this study investigates the environmental impact of lightweight aggregates (LWAs) produced starting from different mixes of different clays with brewery sludge and cattle bone flour ash (CBA), used as poring and fertilizing agents, respectively. The environmental impact was evaluated by means of release tests, insulation capacity, carbon footprint (CFP), and particulate matter emission during pellet firing. Release tests representative of LWAs realistic application showed very high release of phosphate and satisfactory release of potassium. The thermal insulation of the LWAs was tested by thermal imaging camera and resulted highly variable depending on the composition, with the mix containing CBA performing best. This latter composition leads also to the smallest CO₂ equivalent emission, due to the calorific power of CBA, allowing lower consumption of fossil fuels during the LWA production. Finally, total particulate emissions during the thermal treatment resulted similar in terms of mass for all mixes, while differences in terms of particle morphology and composition occurred. Samples containing residue resulted with a quite good release behavior, CFP, and insulation properties, but higher emission of particles, particularly when glass is added.