Construction of a macromolecular structural model of Chinese lignite and analysis of its low-temperature oxidation behavior

The aim of this paper is to analyze the change in the active structure of lignite during the process of lowtemperature oxidation by constructing a molecular structure model for lignite. Using quantum computation combined with experimental results of proximate analysis, ultimate analysis, Fourier transform infrared spectroscopy(FTIR) and X-ray photoelectron spectroscopy(XPS), a structural model for the large molecular structure was constructed. By analyzing the bond lengths in the model molecule, the evolution law for the active structure of lignite was predicted for the process of low-temperature oxidation. In low-temperature oxidation,alkanes and hydroxyls are the primary active structures observed in lignite, though ether may also react. These active functional groups react with oxygen to release heat, thereby speeding up the reaction between coal and oxygen. Finally, the content of various functional groups in the process of lignite low-temperature oxidation was analyzed by infrared analysis, and the accuracy of the model was verified.

Facile synthesis of Cu-doped manganese oxide octahedral molecular sieve for the efficient degradation of sulfamethoxazole via peroxymonosulfate activation

Advanced processes for peroxymonosulfate(PMS)-based oxidation are efficient in eliminating toxic and refractory organic pol-lutants from sewage.The activation of electron-withdrawing HSO_(5)^(-)releases reactive species,including sulfate radical(·SO_(4)^(-)),hydroxyl radical(·OH),superoxide radical(·O_(2)^(-)),and singlet oxygen(1O_(2)),which can induce the degradation of organic contaminants.In this work,we synthesized a variety of M-OMS-2 nanorods(M=Co,Ni,Cu,Fe)by doping Co^(2+),Ni^(2+),Cu^(2+),or Fe^(3+)into manganese oxide oc-tahedral molecular sieve(OMS-2)to efficiently remove sulfamethoxazole(SMX)via PMS activation.The catalytic performance of M-OMS-2 in SMX elimination via PMS activation was assessed.The nanorods obtained in decreasing order of SMX removal rate were Cu-OMS-2(96.40%),Co-OMS-2(88.00%),Ni-OMS-2(87.20%),Fe-OMS-2(35.00%),and OMS-2(33.50%).Then,the kinetics and struc-ture-activity relationship of the M-OMS-2 nanorods during the elimination of SMX were investigated.The feasible mechanism underly-ing SMX degradation by the Cu-OMS-2/PMS system was further investigated with a quenching experiment,high-resolution mass spec-troscopy,and electron paramagnetic resonance.Results showed that SMX degradation efficiency was enhanced in seawater and tap water,demonstrating the potential application of Cu-OMS-2/PMS system in sewage treatment.

MOLECULAR BEAM STUDIES ON OXIDATION OF CO ON Pd WITH DIFFERENT MIXED RATIOS OF P_(CO) TO P_(O2) ~*

Here some steady-state experiments on oxidation of CO on Pd were performed on a molecular beam apparatus. It is found that the characteristics of the rate of CO_2 formation r versus substrate temperature T are dependent on the ratio P=P_(CO)/P_(O2) in the mixed beam. These characteristics are related to the complicated interactions of co-adsorbed CO and O particles on Pd surface.

Oxidative Molecular Layer Deposition Tailoring Eco-Mimetic Nanoarchitecture to Manipulate Electromagnetic Attenuation and Self-Powered Energy Conversion

Advanced electromagnetic devices,as the pillars of the intelligent age,are setting off a grand transformation,redefining the structure of society to present pluralism and diversity.However,the bombardment of electromagnetic radiation on society is also increasingly serious along with the growing popularity of"Big Data".Herein,drawing wisdom and inspiration from nature,an eco-mimetic nanoarchitecture is constructed for the first time,highly integrating the advantages of multiple components and structures to exhibit excellent electromagnetic response.Its electromagnetic properties and internal energy conversion can be flexibly regulated by tailoring microstructure with oxidative molecular layer deposition(oMLD),providing a new cognition to frequency-selective microwave absorption.The optimal reflection loss reaches≈−58 dB,and the absorption frequency can be shifted from high frequency to low frequency by increasing the number of oMLD cycles.Meanwhile,a novel electromagnetic absorption surface is designed to enable ultra-wideband absorption,covering almost the entire K and Ka bands.More importantly,an ingenious self-powered device is constructed using the eco-mimetic nanoarchitecture,which can convert electromagnetic radiation into electric energy for recycling.This work offers a new insight into electromagnetic protection and waste energy recycling,presenting a broad application prospect in radar stealth,information communication,aerospace engineering,etc.

Evaluation of metal-doped manganese oxide octahedral molecular sieves in catalytic reduction of NO_x from cigarette mainstream smoke

A series of Ag,Cu and Co-doped manganese oxide octahedral molecular sieves(OMS-2) were synthesized and evaluated to remove nitrogen oxides(NOx) from cigarette mainstream smoke.The three kinds of catalysts were added to cigarettes for studying the capabilities of reducing NOx from cigarette mainstream smoke.The catalysis and reduction of NO in laboratory were studied.A mechanism for NOx catalytic reduction from burning cigarettes with the catalysts adding to cigarettes was described.The catalysts show excellent catalytic activity for NOx removal,especially the Ag-doped OMS-2 catalyst.0.5%(mass fraction) Ag-doped OMS-2 catalyst has the best ability to remove NOx from cigarette mainstream smoke.The use of Ag-doped OMS-2 as catalyst for removing carcinogenic compounds from cigarette smoke will be an effective strategy to protect the environment and public health.

Seed-induced synthesis of small-crystal TS-1 using ammonia as alkali source

Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2 adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS- 1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.

Relationship between reaction rate constants of organic pollutants and their molecular descriptors during Fenton oxidation and in situ formed ferric-oxyhydroxides

Fenton oxidation is a promising water treatment method to degrade organic pollutants. In this study, 30 different organic compounds were selected and their reaction rate constants（k） were determined for the Fenton oxidation process. Gaussian09 and Material Studio software sets were used to carry out calculations and obtain values of 10 different molecular descriptors for each studied compound. Ferric-oxyhydroxide coagulation experiments were conducted to determine the coagulation percentage. Based upon the adsorption capacity,all of the investigated organic compounds were divided into two groups（Group A and Group B）. The percentage adsorption of organic compounds in Group A was less than 15%（wt./wt.）and that in the Group B was higher than 15%（wt./wt.）. For Group A, removal of the compounds by oxidation was the dominant process while for Group B, removal by both oxidation and coagulation（as a synergistic process） took place. Results showed that the relationship between the rate constants（k values） and the molecular descriptors of Group A was more pronounced than for Group B compounds. For the oxidation-dominated process,EHOMOand Fukui indices（f（0）_x, f（-）_x, f（＋）_x） were the most significant factors. The influence of bond order was more significant for the synergistic process of oxidation and coagulation than for the oxidation-dominated process. The influences of all other molecular descriptors on the synergistic process were weaker than on the oxidation-dominated process.

Catalytic oxidation of carbon monoxide, toluene, and ethyl acetate over the xPd/OMS-2 catalysts： Effect of Pd loading

The Pd catalyst supported on cryptomelanetype manganese oxide octahedral molecular sieve （OMS- 2） were prepared. The effect of Pd loading on the catalytic oxidation of carbon monoxide, toluene, and ethyl acetate over xPd/OMS-2 has been investigated. The results show that the Pd loading plays an important role on the physicochemical properties of the xPd/OMS-2 catalysts which outperform the Pd-free counterpart with the 0.5Pd/ OMS-2 catalyst being the best. The temperature for 50% conversion was 25, 240 and 160 ℃, and the temperature for 90% conversion was 55,285 and 200 ℃ for oxidation of CO, toluene, and ethyl acetate, respectively. The low- temperature reducibility and high oxygen mobility ofxPd/ OMS-2 are the factors contributable to the excellent catalytic performance of 0.5Pd/OMS-2.

Remarkable promotion effect of trace sulfation on OMS-2nanorod catalysts for the catalytic combustion of ethanol

OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using Mn SO4（OMS-2-SO4） and Mn（CH3COO）2（OMS-2-AC） as precursors. SO4^2--doped OMS-2-AC catalysts with different SO4^2-concentrations were prepared next by adding（NH4）2SO4solution into OMS-2-AC samples to investigate the effect of the anion SO4^2-on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO4 catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO4^2-doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO4^2-（SO4/catalyst = 0.5% W/W）. The samples were characterized by X-ray diffraction（XRD）, field emission scanning electron microscopy（FE-SEM）, transmission electron microscopy（TEM）, X-ray photoelectron spectroscopy（XPS）,inductively coupled plasma optical emission spectroscopy（ICP-OES）, NH3-TPD and H2-TPR techniques. The results showed that the presence of a suitable amount of SO4^2-species in the OMS-2-AC catalyst could decrease the Mn–O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO4 compared to OMS-2-AC is due to the presence of some residual SO4^2-species in OMS-2-SO4 samples.

Effects of ozonation and coagulation on effluent organic matter characteristics and ultrafiltration membrane fouling

Effluent organic matter （EfOM） is the major cause of fouling in the low pressure membranes process for wastewater reuse. Coagulation and oxidation of biological wastewater treatment effluent have been applied for the fouling control of microfiltration membranes. However, the change in EfOM structure by pre-treatments has not been clearly identified. The changes of EfOM characteristics induced by coagulation and ozonation were investigated through size exclusion chromatography, UV/Vis spectrophotometry, fluorescence spectrophotometry and titrimetric analysis to identify the mechanisms in the reduction of ultrafiltration （UF） membrane fouling. The results indicated that reduction of flux decline by coagulation was due to modified characteristics of dissolved organic carbon （DOC） content. Total concentration of DOC was not reduced by ozonation. However, the mass fraction of the molecules with molecular weight larger than 5 kDa, fluorescence intensity, aromaticity, highly condensed chromophores, average molecular weight and soluble microbial byproducts decreased greatly after ozonation. These results indicated that EfOM was partially oxidized by ozonation to low molecular weight, highly charged compounds with abundant electron- withdrawing functional groups, which are favourable for alleviating UF membrane flux decline.

Temperature sensitivity of organic compound destruction in SCWO process

To study the temperature sensitivity of the destruction of organic compounds in supercritical water oxidation process （SCWO）, oxidation effects of twelve chemicals in supercritical water were investigated. The SCWO reaction rates of different compounds improved to varying degrees with the increase of temperature, so the highest slope of the temperature-effect curve （/max） was defined as the maximum ratio of removal ratio to working temperature. It is an important index to stand for the temperature sensitivity effect in SCWO. It was proven that the higher imax is, the more significant the effect of temperature on the SCWO effect is. Since the high-temperature area of SCWO equipment is subject to considerable damage from fatigue, the temperature is of great significance in SCWO equipment operation. Generally, most compounds （/max 〉 0.25） can be completely oxidized when the reactor temperature reaches 500~C. However, some compounds （/max 〉 0.25） need a higher temperature for complete oxidation, up to 560~C. To analyze the correlation coefficients between/max and various molecular descriptors, a quantum chemical method was used in this study. The structures of the twelve organic compounds were optimized by the Density Functional Theory B3LYP/6-311G method, as well as their quantum properties. It was shown that six molecular descriptors were negatively correlated to imax while other three descriptors were positively correlated to imax. Among them, dipole moment had the greatest effect on the oxidation thermodynamics of the twelve organic compounds. Once a correlation between molecular descriptors and imax is established, SCWO can be run at an appropriate temperature according to molecular structure.