Mechanisms and kinetic studies of OH-initiated atmospheric oxidation of methoxyphenols in the presence of O2 and NOx.

Methoxyphenols, as the main products and tracers of biomass burning, have been demonstrated to play an important role in the formation of secondary organic aerosols. However, their chemical transformation and migration in the atmosphere haven't been well characterized. In this study, detailed gas-phase reaction mechanisms and kinetics of three representative methoxyphenols (guaiacol, creosol and syringol) with OH radicals were investigated by using density functional theory (DFT). The initial reactions of methoxyphenols with OH radicals proceed via two different patterns, including OH-addition and H-atom abstraction. Subsequent reaction schemes of the active intermediates in the presence of O2/NOx are thoughtfully modeled. Catechol, methyl glyoxylate, malealdehyde and carbonyl or carboxyl compounds were confirmed as the dominant oxidation products for guaiacol. As a supplementary study, the formation pathways for the expected products nitroguaiacol and nitrocatechol were presented in high-NO2 conditions. Total and individual rate coefficients are calculated using the MESMER program at 294 K and 1 atm. The lifetimes of guaiacol, creosol and syringol were estimated to be 4.27, 3.56 and 2.98 hours, respectively, which are strongly competitive with the solar photolysis of methoxyphenols.

Developing energy-efficient N-doping technology to controllably construct N-Ru2P@Ru nanospheres for highly efficient hydrogen evolution at an ampere-level current density.

The N-doping strategy plays a vital role in optimizing electrocatalytic performance, but it often requires high-temperatures accompanied by the emission of irritating gases, which is contrary to the concept of energy saving and environmental protection. Based on this, this work innovatively uses the quenching of waste heat and the non-equilibrium state of materials to realize controllable N-doping. Notably, N dopants stimulate metal-like electroconductivity and accelerate the alkaline HER kinetics by optimizing the electronic structure of Ru2P. Surprisingly, the hydrophilic Ru core and the N-Ru2P shell with a low HER reaction energy barrier synergistically expedite hydrogen release. As anticipated, the current density of N-Ru2P@Ru (963 mA cm-2) is 2.6-fold that of Pt/C (359 mA cm-2) at 150 mV. Overall, the novel N-doping technology greatly simplifies material preparation procedures and reduces energy consumption. Moreover, this unique N-doping strategy provides a new idea for optimizing the catalyst structure and reaction kinetics.

Spent shell as a calcium source for constructing calcium vanadate for high-performance Zn-ion batteries.

In this article, waste shell is directly used as a raw material to synthesize CaV3O7 as a cathode for aqueous zinc ion batteries. The obtained cathode material exhibits better performance than that of CaV3O7 prepared from pure calcium carbonate as a raw material. At 0.1 A g-1, the CaV3O7 prepared by spent shell as a calcium source displays a highly reversible discharge capacity of 373 mA h g-1. A high initial discharge capacity of 177.7 mA h g-1 can be gained at 5.0 A g-1, and the specific capacity remains at 133.3 mA h g-1 with a capacity retention of 75% after 3000 cycles. This work may spark inspiration for energy storage and generate more effective routes for recycling solid waste.

Vanadium recovery by electrodialysis using polymer inclusion membranes.

Industrial applications and environmental awareness recently prompted vanadium recovery spell from secondary resources. In this work, a polymer inclusion membrane containing trioctylmethylammonium chloride as carrier was successfully employed in electrodialysis for vanadium recovery from acidic sulfate solutions. The permeability coefficient of V(V) increased from 0.29 µm·s-1 (without electric field) to 4.10 µm·s-1 (with the 20 mA·cm-2 current density). The transport performance of VO2SO4-, which was the predominant species containing V(V) in the acidic region (pH <3), was influenced by the aqueous pH value and sulfate concentration. Under an electric field, a low concentrated H2SO4 solution (0.2 M) effectively stripped V(V) from the membranes, avoiding the requirement of a highly concentrated H2SO4 without electric field. Under the optimum conditions, the permeability coefficient and flux reached 6.80 µm·s-1 and 13.34 µmol·m-2·s-1, respectively. High selectivity was observed for the separation of V(V) and Mo(VI) from mixed solutions of Co (II), Ni (II), Mn (II), and Al (III). Additionally, the separation between Mo(VI) and V(V) was further improved by adjusting the acidity of the stripping solution. The V(V) selectivity for the resulting membrane was higher than that of commercial anion exchange membranes.

Effect of Functionalized Carbon Microspheres Combined with Ammonium Polyphosphate on Fire Safety Performance of Thermoplastic Polyurethane.

In this article, carbon microspheres (CMSs) synthesized by the hydrothermal method and CMSs-Fe (with Fe3+ adsorbed on the surface of CMSs) were combined with ammonium polyphosphate (APP) to achieve the fire safety improvement of thermoplastic polyurethane (TPU). The fire safety performance of TPU composites was investigated by the cone calorimeter test, microscale combustion calorimeter test, thermogravimetric analysis/infrared spectrometry, Raman spectrometry, X-ray photoelectron spectroscopy, and scanning electron microscopy. The results showed that CMSs and CMSs-Fe can improve the fire safety performance of TPU/APP composites and the effect of CMSs-Fe was better than that of CMSs. The peak heat release rate of the sample containing 0.25 wt % CMSs and 7.75 wt % APP was 16.7% lower than that of the sample containing 8.00 wt % APP, and the content of toxic gases was also reduced in the fire smoke. Also, total heat release and total smoke release of the sample containing CMSs-Fe were 54.7% and 11.6%, respectively, lower than those of the sample containing 0.25% CMSs. It confirmed the contribution of CMSs to the flame retardant system, and the performance of CMSs is improved by adsorbing Fe3+.

Synthesis of nanoparticle-assembled Zn3(VO4)2 porous networks via a facile coprecipitation method for high-rate and long-life lithium-ion storage.

A simple coprecipitation route followed by a calcination process was developed to prepare 2D hierarchical Zn3(VO4)2 porous networks formed by the crosslinkage of monolayered nanoparticles. As a promising anode for lithium ion batteries, the electrochemical performance of Zn3(VO4)2 was investigated. At a current density of 1.0 A g-1, the Zn3(VO4)2 porous networks could register a high reversible discharge capacity of 773 mA h g-1 and the capacity retention was 94% after 700 cycles. Moreover, a remarkable reversible discharge capacity of 445 mA h g-1 was achieved at a current density of 5 A g-1 after 1200 cycles. Even at a higher current density of 10.0 A g-1, a high reversible capacity of 527 mA h g-1 could be delivered, which still remained at 163 mA h g-1 after 1200 cycles. This superior performance is attributed to the unique 2D porous networks with a stable structure. This work shows a new avenue for facile, cheap, green, and mass production of zinc vanadate oxides with 2D porous hierarchical networks for next-generation energy conversion and storage devices.

A facile route to prepare mixed transition metal oxide yolk-shell microspheres for enhanced lithium storage.

A coordination co-precipitation route followed by a calcination process was developed to prepare mixed transition metal oxide microspheres with a yolk-shell structure. ZnCo2O4, NiCo2O4, MnCo2O4, ZnMn2O4 and CoMn2O4 have been successfully fabricated, which demonstrates the universality of this route. As a promising anode for lithium-ion batteries (LIBs), ZnCo2O4 was investigated as a typical example, which showed a remarkable reversible capacity of 1063 mA h g-1 after 50 cycles at a current density of 200 mA g-1 and a good rate capability of 839 mA h g-1 after 200 cycles at a large current density of 900 mA g-1. This work shows the extensive potential of a general route for the synthesis of yolk-shell microspheres for next-generation energy conversion and storage devices.

Synthesis and electrochemical properties of nanostructured LiCoO2 fibers as cathode materials for lithium-ion batteries.

Nanostructured LiCoO2 fibers were prepared by the sol-gel related electrospinning technique using metal acetate and citric acid as starting materials. The transformation from the xerogel fibers to the LiCoO2 fibers and the nanostructure of LiCoO2 fibers have been investigated in detail. The LiCoO2 fibers with 500 nm to 2 mum in diameter were composed of polycrystalline nanoparticles in sizes of 20-35 nm. Cyclic voltammetry and charge-discharge experiments were applied to characterize the electrochemical properties of the fibers as cathode materials for lithium-ion batteries. The cyclic voltammogram curves indicated faster diffusion and migration of Li+ cations in the nanostructured LiCoO2 fiber electrode. In the first charge-discharge process, the LiCoO2 fibers showed the initial charge and discharge capacities of 216 and 182 (mA.h)/g, respectively. After the 20th cycle, the discharge capacity decreased to 123 (mA.h)/g. The X-ray diffraction and high-resolution transmission electron microscopy analyses indicated that the large loss of capacity of fiber electrode during the charge-discharge process might mainly result from the dissolution of cobalt and lithium cations escaping from LiCoO2 to form the crystalline Li2CO3 and CoF2 impurities.